博 	
  士 	
  論 	
  文

再利用可能な水銀反応剤カルバボラニル水銀塩の創製と抗水カビ活性を有するオリダマイ
シン A の誘導体合成への応用

徳島文理大学大学院薬学研究科
薬学専攻	
  博士課程山 崎 直	
  人

指導教授	
  	
  今川	
  洋
平成三十年提出

目次
略号
緒論

1

第一章	
 	
  	
  	
  	
  カルバボラニル塩化水銀の創製と応用
	
  	
 

第一節	
  	
  序説

11

	
  	
 

第二節	
  	
  カルバボラニル塩化水銀の創製

13

	
  	
 

第三節	
  	
  カルバボラニル水銀触媒を用いたアリル選択的な 1,3-ジエン環化
反応の開発

	
  	
 

	
  	
 

17

第四節	
  	
  小括

第二章	
  	
  	
  	
 

22

ポリシロキサン架橋型カルバボラニル水銀トリフラートの開発

	
  	
 

第一節	
  	
  序説

23

	
  	
 

第二節	
  	
  カルバボラニル塩化水銀の物性研究

27

	
  	
 

第三節	
  	
  ポリシロキサン架橋型カルバボラニル水銀トリフラートの開発

30

	
  	
 

第四節	
  	
  不均一系反応の基質一般性検討

35

	
  	
 

第五節	
  	
  小括

41

第三章	
  	
  	
  	
 
	
  	
 

Myers 型還元的脱酸素化反応の開発

第一節	
  	
  序説

42

第二節	
  	
  カルバボラニル水銀触媒を用いた Myers 型還元的脱酸素化反応
の開発
	
  	
 

第三節	
  	
  小括

第四章	
  	
  	
  	
 
	
  	
 

55

(±)-Oridamycin A の全合成と類似体の合成および活性評価

第一節	
  	
  序説
第二節	
  	
  (±)-Oridamycin A および C3-epi 体の合成および生物活性評価

	
 

46

第三節	
  	
  小括

56
60
67

総括

68

実験の部

69

参考文献

152

謝辞

159

略号
Ac

acetylAcOEtethyl acetate

AgBF4silver(I) tetrafluoroborate

AgClsilver(I) chloride

AgOTfsilver(I) trifluoromethanesulfonate

AIBN

2,2'-azobis(isobutyronitrile)

Ar

aryl

AuCl

gold(I) chloride

AuCl3

gold(III) chlorideaq

aqueous solution

Boc

tert-butoxycarbonylBnbenzylBsbenzenesulfonyl

Bu

butyl

t-Bu

t-butyln-BuLin-butyllithium

t-BuLit-butyllithium

CeO2

cerium(IV) oxide

CIMS

chemical ionization mass spectrometryDDQ

2,3-dichloro-5,6-dicyano-p-benzoquinone

DEAD

diethyl azodicarboxylate

DMAP

4-dimethylaminopyridine

DMF

N, N-dimethylformamide

DMP	
  	
  	
  	
 

dess-martin periodinane

DMSO

dimethylsulfoxide

DTBM

di-t-butylmethoxyphenyl

EC50

mediam effect concentrationeeenantiomeric excess

EDX

energy dispersive x-ray spectroscopy

EIMS

electron impact mass spectrometryeqequivalent

Et

ethyl

Et2O

diethyl ether

EtOH

ethanol

HAPhydroxylapatite

HClhydrogen chloride

HgO

mercuric(Ⅱ) oxide

Hg(OAc)2

mercuric(Ⅱ) acetate

Hg(OTf)2

mercuric(Ⅱ) trifluoromethanesulfonate

Hg(OTFA)2

mercuric(Ⅱ) trifluoroacetate

HgSO4

mercuric(Ⅱ) sulfate

HOTftrifluoromethanesulfonic acidICliodine monochloride

IPNBSH

N-isopropylidene-N’-2-nitrobenzenesulfonyl hydrazine

KBr

potassium bromide

LD50

medium lethal dose

LHMDS

lithium hexamethyldisilazide

LiBrlithium bromide

Li2CuCl4

dilithium tetrachlorocuprate(II)MALDI

matrix assisted laser desorption/ionization

Mbs

p-methoxybenzenesulfonylMCmicrocapsulem-CPBAm-chloroperoxybenzoic acidMW

microwave

Me

methylMeHgClmethylmercuric(II) chloride

MeI

	
 

iodomethane

MIC	
  	
  	
 

minimum inhibitory concentration

MOM

methoxymethylMts2-mesitylenesulfonyln-normal-NaBH4	
  	
  	
  	
 

sodium borohydride

NaBrsodium bromide

NaClsodium chloride

NBSH

2-nitrobenzenesulfonyl hydrazide

NOE

nuclear Overhauser effectNs

2-nitrobenzenesulfonylNunucleophileOMemethoxy

OsO4

osmium(VIII) oxide

PEG

polyethylene glycol

PG

protective groupPhphenylPI

polymer-incarserated

PhHgClphenylmercuric(II) chloride

PhHgOAcphenylmercuric(II) acetatePMBp-methoxybenzyl

PPh3

triphenylphosphineppm

parts per million

Piv

pivaloylPypyridinequant	  	  	 quantitative

rtroom temperature

SEGPHOS

5,5'-bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole

SEM

scanning electron microscope

SM	
  	
  	
  	
  	
 

starting materials

SPhos

2-dicyclohexylphosphino-2',6'-dimethoxybiphenylt-tertiary-

TBAF

tetrabutylammonium fluoride

TBStert-butyldimethylsilyl

TBDPS

tert-butyldiphenylsilylTemp.

temperature

TEOS

tetraethyl orthosilicate

TFE

2,2,2-trifluoroethanol

TMU

tetramethylurea

TMS

trimethylsilyl

TMSBrtrimethylsilyl bromide

TMSOTftrimethylsilyl trifluoromethanesulfonate

TMSE

2-(trimethylsilyl)ethyl

TOFMS

time of flight mass spectrometry

p-Tol

p-methyl phenyl

Tftrifluoromethanesulfonyl

Tf2O

trifluoromethanesulfonic anhydride

TfOH

trifluoromethanesulfonic acid

THF

tetrahydrofuranTsp-toluenesulfonyl

jr
 9>[yG|Henbest!#3*5'(+[yDERzc

DJERAcN"t
7/

IZ,Scheme 1.1) 1972 O, Semenovsky|[y-2.3'4vwHgOTFA2" 4

6 aFT{<ZY!Hx`DER?b|02&5`DA[yGERAKe.2) 1980 O:|Corey  Hoye|Snider

FTDJl

U%$3,]S"g±-Aphidicolin

9±-Ancistrofuran12±-Velloziolone14FTfi?bLk
=

)3

|L

!.3)

Scheme 1 [yGqo"b#3*5'(+[yD6n[yDER

Henbest, H. B. et al (1959)
Traylor, T. G. et al (1963)
R1

R2

R3

HgX2
ROH

R4
1

R1 HgX
R3
R2
RO R4
2

NaBH4
Hg (0)

RO R4
3

O

NaBH4

O

R1 H
R3

R2

Semenovsky, A. V. et al (1972)
O

Hg(OTFA)2
TFAOHg4

Hg (0)

H
562% (2 steps)

H
6

Corey, E. J. et al (1980)
CO2Me
OPO(OEt)2
1) Hg(OTFA)2
2) NaCl aq.
TBSO

7

60%

ClHg
TBSO

H
8

 8X|1983 O|QfiM@;WVp^uh 15

OH

CO2Me
O
H

OH

H
HO
HO

H (±)-Aphidicolin (9), ±-Lansic Acid 17FTfi

16 C_d02&5`DA"s\|PB3$,wZm![y-2.17-HgOTf2"zc.4)

1

Hoye, T. R. et al (1981)
1) Hg(OTFA)2

OH

O

O
O

O

2) KBr3) NaBH4
88% (3 steps)

10

O

H
11

H
(±)-Ancistrofuran (12)Snider, B. B. et al (1992)
OOHO

1) Hg(OTFA)2
2) KBr

O

O

BrHg

H

H
13

78%

10

OH

(±)-Velloziolone (14)

Nishizawa, M. et al (1983)

CO2H

SO2 p-Tol

SO2 p-Tol

1) Hg(OTf)2•PhNMe2(1.2 eq)
2) NaCl aq.

H

ClHg

H
16

H

>X0BRXHgOTf2 CJ596?4
J

H

HO2C

H

74% (2 steps)

15

H(±)-Lansic Acid (17)

XF7@LO3Scheme 2Y1X2000 <XD/89G;,M:X+-Gelsemine2027@SNX18 I56? HgOTf2 J
19 EP.5) 2010 <XSnyder *-&X$

HgOTf2 JT@XW=QI.A!+"'I56?VK)+ 22 , –-4-Isocymobarbatol2327@

.6)

Scheme 2 HU#)%(-#J

7@LO1

Yokoshima, S.; Fukuyama, T. et al (2000)
O

N

O

O

MOM
N

OH
18

1) Hg(OTf)2•PhNMe2

N

O

MOM

N

O
NH

N

2) NaCl aq
3) NaBH4, NaOH
BnNEt3Cl
63% (3 steps)

O

O
19

2

(+)-Gelsemine (20)Snyder, S. A. et al (2010)
1) Hg(OTf)2 (1.1 eq)
Ligand 22 (1.2 eq)
then NaBr

OMOMBrOMOM 3) HCl, THF

21

Br

O

Br

2) Br2, LiBr
O2, Pyridine

n-C4H9O
NOH

H

n-C4H9O(−)-4-Isocymobarbatol (23)N

22

48% (3 steps), 90% ee@"i\Jung, |S%l.<>5

HgOTf2 )FxwsobVrsCNc)RO'Fig. 1.7) h]}~Z"w
_QX{%('–-Thallusin29CNcHgOTf2 $'6;,=vI
J`)Fx.8)
Hayashi, Y. et al (2005)

Jung, Y. H. et al (2017)

Nishikawa, K. et al (2017)

O

Me
N

MeO
O

O

N

OH

H

HO

R = n-Bu: (–)-Lepadiformine A (25)
R = Et: (–)-Lepadiformine B (26)(–)-Codonopsinine (27)

HO

OH O
epi-EI-1941-2 (24)R

Me

Yamamoto, H. et al (2014)

Sunazuka, T.; Omura, S. et al (2009)

CO2H

N

O

O

H
NH

HN

O

N
H

N

O

N
O

H
N
H

O
N
H

OMe

CO2H

N

CO2H
O

S
H
H

Bottromycin A2 (28)Fig. 1 IYn2;4:>2


EPA

NcIY Trostx%(NcB

fP+28,037>9) ja#+9;-vUze'vUg.;>=/712;>

TJ`GIY(–)-Thallusin (29)%y[

puA?^n

!_"tDvU)qdLJ`k)&!H'$

"EFxLnWy`xK&*
HgOTf2 WJ`ymMj'
3







Scheme 3 hN"o#6(9=DG\

1) Thomas, R. J. et al (1938): HgSO4
2) Stacy, G. W. et al (1955): HgO
Hg (II) salt
RO

H
H2SO4/H2O

R

 H

FR



 HgSO4 "o#6(9h=DG\{JScheme 3.10) zFhHgO"Po[~PElaK

PG\qfb`_
%7#TMU"iD

e>

q



@

50 mol% HgO "]g.11) }jdG\Elr

2002 W, HgOTf2  3 X ,-43+6
PEl"OVaK

4.12) ZHgOTf2 P"o\U

CH3
31

30

"BScheme#6(9CQAmFG\kukuwIY^G

PLc1000≥TON"s#5;6:$9mFG\"

y.13)

 Scheme 4 h-504;-"o#6(9PG\

Nishizawa, M. et al (2002)
Hg(OTf)2•3TMU(5 mol%)H2O (3.0 eq)

O

CH3CN/CH2Cl2
rt, 12 hquant.

32

…….

(1)

…….

(2)

33

Nishizawa, M. et al (2003)
OMe Hg(OTf) •3TMU
2(0.1 mol%)n-C4H9OMe

CH3CN, rt, 3 h
99%

34

OMe

n-C4H9 OMe
35#5;6:$9mFG\HgOTf2#6(9 σpπM? 36 "Y^,Friedel-Crafts MmFG\

/.6h<? 37 "n^

|

.

!

in situ qn-506&83*9)629HOTf18-9F!
ST 3 t'+&9<? 38 "vpxhFG\

4|PG\



OMe

OMe

OMe

n-C4H9

TfOH

OMe
36

EjHgOTf2

+

TfOHg

TfOHg

(TfO)2Hg

n-C4H9 OMe

TfO-

37


35

n-C4H9 OMe38 Hg(OTf)2
W!3$5`C?F];YZ[cj/15

#5-25LW.3+"5&04*%`C?F

@IFig. 2.14) Kbj>_ARN Indolozocine  Benzodiazepine i
OQ\:W.15)

Imagawa, H. et al (2004)

Ph

Yamamoto, H. et al (2007)

Hg(OTf)2(1 mol%)O

NHTs>99% ee 41

40

Van der Eycken, E. V. et al (2009)
O
N
R1
NH

R2

R1
N

O

NH

up to 95%

R3

44
Indoloazocine coreR1
(2.2 eq)

NH2

Hg(OTf)2(1 mol%)Ba

Td,2/16,`C

NuH

H
N

R1

OH

R
N
46

R1

W!3$5`C?F 48 `CV=?F

eDHP!3'5
Scheme 542

Benzodiazepine core

7Jj2008 DjgU!3$5`C)#%3
?FBa

80%
98% ee45

Fig. 2  Td,2/16,`C

3(63 47

NTs

CH2Cl2NH2R

CH2Cl2, MW

43

O

Maiti, G. et al (2012)

R3
Hg(OTf)2(5 mol%)R2

R

S

C 6H 694%

39

Hg(OTf)2(1 mol%)

O

O

Ph

hSG^



Scheme 5.16) M?FfX

`C?F9I<

8kW!23!3(63V=?F
Hg(OTf)2(0.1 mol%)(CH2Cl)2, rt

+ H2O

Nu

48

47
Nu = NTs, C, O

5

j!23!

TfO-

Hg(OTf)2

HgOTf

OH

NuH
49

D7?Y'

50

Nu

51

HOTf

プロトン化

H
O+
H

48
Hg(OTf)2
H 2O

脱水銀化

)S.%(#)6"#ET9</

X1 HgOTf2 2H
Y>D

OH

Nu

プロトン化サイト

HgOTf

YEM

Q;7?Z9R+N@Q;5FO:YYEUQ;3,B&''!*'G67?=V.17) CSYPW'($amine60 08A4I

J Communesin F57 Palau’Scheme 6.18)

Scheme 6 &''!*'G67?8AKL?I-

Harmata, M. et al (2011)

HO

HO
MeO
Me

OMe
OMe
52

Hg(OTf)2(2 mol%)MeO

C6H6, 70 °C
15 min

Me

O
O

OMe

H

OMe

63%

Elisapterosin B (54)53

Funk, R. L. et al (2012)

O

OH
Boc
OMe
HN O

NH
N H
Me
55

Hg(OTf)2(2.5 mol%)

Boc
N O

N

OMe
N

H

CH2Cl2
rt, 16 h
86%

NH
N H
Me
56

NH
N H
Me
(±)-Communesin F (57)

Namba, K. et al (2015)

O



Ts N
H 2N
HO

OH
58

Hg(OTf)2(2 mol%)O

CH3NO2

Ts

N

HN
H 2N

E

N
H

84%

OH

HN

N
N
HN

59

6

O

N

H

N
H
E

H

HO Cl
Palau’amine (60)NH2 9z¹2010 k¹nfj~# 1,3-Io+)6 61  2 mol% HgOTf2 'O
%¹Q9/-56\PB 62¸Ts%'¥JScheme 7.19)@´i_§cAu, Ag, Fe ¹s E, Z rB'Lp
&$¹µ_¢r





«

w&bD%. 20)

Scheme 7 µ,3028,§c' 1,3-+)6PSq
Hg(OTf)2(2 mol%)

NHTs

N
Ts
89% 62 (ビニレン型)

CH2Cl2, rt61¹µ§cSq

r

l

N
Ts
63 (アリル型)%¹£¡ 61 #(34\PB 63 ±uPSq¶tº¹{d>Eµ_'Sq,
%A! 62  63 V';%ºY·g,£¡¹y¦µSqM*4.12-4µ_ 64 '©¨7Vs%¹63 ±uPSq'¶Scheme 8.21)

*4.12-4_PµN¤q¹9ª®%º
Scheme 8 *4.12-4_PµN¤q9

H

64

HgCl
(4 mol%)/AgOTf(4 mol%)
N
Ts

NHTs

CH2Cl2, rt

61

>99%

 :®Sq'^W##"¯'¦L%G

N
Ts

63

62

¹|~`=h!¹µ¤XC<U[&Fig. 3.22) ~¹´iµ"

µPV?vJ"xJ#?HmR`'<¦F¬%%º



¹}PeK³G°Z9²Sq¦

Lg­!¹]

%µSqMC¹

%º
7

g­a

(!9O(2013z201783@GzD5%
X2 z2F

+2

zzz129^R;:
AM
2 z2F

z2F

IX8KzYVSX
(J\pu_q&62\pu_q

I(JXz@GN)z?Bz,B(J0zE>z*'>

$(JN"[2QU=d{f@G/$(J[2QU
\uhli@G

8(J$P
grwa{u|x`gyL< }

H

(JC>[2QU
 mjuskp{
Zot]veyX@GPP

47A#WX(JC>X2
(J1.[-UTU
nwcb@GFig. 3 kf~iw

 

;]

kH_D'euFXH_DCukT

euy'AEkr*475+2-/47'Z%^%&#M

J$.71kH_WF

kH_DPI?Cu%am{}K`z|_u'bAFig. 4

+ 3
2./7(-(-2076%5

+3

+ 3' + 3 8
073"$

+3 8*1)2./71&,

!#43Fig. 4 kFKq<u%J$

RtUvUNEPSN"%klg9GQY=[kVnk\o8B6:dA!@s%.23) kB<uqOkH_D"k\hLj$(/3),027p#%&#'kH_WF><u]kH_D'PI6?Cu%am{}'xc

8 %8036/8kV 64 !It

?T=N[Kv!J`

64

oqMXwsoXwdP"]eAkV\E

64 !?m\475<

5$+Yj\D

47)9&(;^_SOp!z!H 66 !LScheme 9.24) 66 , hHuk

Gaxk-726<-WN[Cb[t 47)9&(;fiU%8036/8k-726<-vN[\~@}



Scheme 9 47)9&(;fiU%8036/8k-726<-v~@}

HgOTf
P

66

CH2Cl2, rt
99%
Recovery of 66 >99.999%

65: ポリシロキサン(20 mol%)

OH
NHTs

P

 kWN[v=r

N
Ts
67

64 -726<-!W#78)9&(; 68 1.6*.lgK 69 n|RZ]N[!v.25) s]o 70  Myers U|MN[B#8'; 71 s]
OQ



!y

N[K

68 :;4,-N[Scheme 10cN[v{64 S

H





]e~>}

Scheme 10 Myers UFwMN[v~>}

Ts
OTBDPS
R

R'

N
H

H
N
69

Boc
Boc

H
N

R

N

Ts

HCl in AcOEt
Neutralsilica gel

R'

70

68

64

9

R

R'

71

HgCl
(5 mol%)H
AgOTf(5 mol%)H

Recovery of 64>95% yield



V04CF2@-@

V64 5<!>3E

W8CFV74 :N>3BRCFJ7

Oridamycin A74,04

DGA6
Q;S

W

49

V64 P%"$(=@3U04&(
@

'#?./2

 Oridamycin A  C3-epi-Oridamycin A ,04O4

Scheme 11.

49R

V8LI1HMW

Scheme 11 ±-Oridamycin A ,04T)*04>3K+I1HH
TBDPSO

PMBO

64(10 mol%)
AgOTf (10 mol%)

then
TBAF
2 steps 80%
72

HgCl
OH
NH

H
PMBO

Recovery of 64 >95%

73

HO
HO2C

H

(±)-Oridamycin A (74)10> /;5794;WMx¤Kg     > b 2007 aªMarks '&ªHe 1,3-1-<MO*NgUXMNg
VQ)Scheme 12.26) 1,3-1-< 75 ¦CGCThNMe22 X*}L(ª¡j+:;TMD 76ig*k8m^h£`(i(Ng(«dpªsNg]OF_"{)

'ªrOiJ)

aªToste '0;=6
*VQ.27) sNg©

ªyhª?n£Bt¥D*
GZcMD 79A

%3:,«fª2011

I?n 1,3-1-<MNg

i(>oªB¢OC¡jh¨*vNg(«!ªToste 'Ppq Nájera '0;=6$
£`WPh3PAuOTf, FeCl3, InBr3 *(.20)  1,3-1-<MNg*VQªB¢OC¡jhR¨Puz





. B¢

OChD|S(ª)'-+:;¥D$+:;/2.<u@§D*Ng(#ª)'[\hiw

EY(#

l~)(.28)
Scheme 12 aªVQ) 1,3-1-<MNg
Marks, T. J. et al (2007)(CGC)Th(NMe2)2

Si

+
NH2

C6D6, 60 °C, 3 h

NH

NH

75

95% (76:77 = 93:7)

76 (アリル体)

77 (ビニレン体)

Th

NMe2

N
NMe2
t-Bu
(CGC)Th(NMe2)22 examples
Toste, F. D. et al (2011)
R(R )-DTBM-SEGPHOS(AuCl)2 (3 mol%)

R
NH
O S
O
(Mbs基)

AgBF4 (6 mol%)(l )-menthol (2 eq)
OMe

42-96%

R

R

R

R
N
Mbs

79 (E/Z mixture )up to 95% ee

78

11

+
(79:80 = 8:2)

N
Mbs
80
up to 53% ee5aToste IbcXuwRUe 1,3-)%4 81  HgOTf2 N"lC
F5.-34KnE; 84

o\

"LJ

HgOTf2

OS?8{H"=>skZE



|T

o\



 84

ro

"A_v



-OTf

HgOTf

Hg(OTf)2
n NHTsCH2Cl2

n

n N

Ts

82

81

+

H

83

N
Ts

up to 98%84 1,3- 
Bulky



HgOTf
H

HOTf
n N

n N

n NHTs

TfOHg
85

.29)

1,3-)%4nEGY

Hg(OTf)2
n NHTsn = 1, 2F5EHm

Scheme 13 ^QGY0'-*/j'+&4PQEDf2 y'+&46;Scheme 13 jMNScheme 13.19) eGY

Ts

Ts

Hg

+

Hg

Bulky
86

 ~}eGYih"|T

Bulky

nN

Ts

Bulky

87

88

@jGYB",($4K]snEGY"`rt[Ws=:dx8{H"]skZE#12KnE; 88-OTf

7o\m

!#12VjM!86  87 "zq

| <g9~}V

j"p 1,3-)%4nEGYr"12L .B7<@6B`V¨T ®h­¨`?5B®9,6B¨`(Table 1¯kfbZo({¡'9,6B¨`pVyM`>3201Zo30)(Y®Zo(¢¯¦§9,6B¨89HOTf "`V9,6B¨90
AgOTf [(Zo®V_£ 61 $*AB^VN 63 
r
2¯

¢

&!® 1:1 86CF^VN 62

rEntries 1,

, #%h­ZoS`V:F39B-D9,6B¨91(Zo({¡Entry 3¯®Zoj"bUz#&{¡(\
xqi(P®¥spa¯

Table 1 9,6B¨ZoS(RZoyM{¡
Hg-reagent(5 mol%)NHTs
61

Additive (5 mol%)
CH2Cl2, rt

Hg-reagent

Entry

N
Ts

+

N
Ts

63

62

AddtiveTime

Yielda (63 : 62)b1

HgOAc (89)

HOTf

72 h

97% (49 : 51)

2

HgCl (90)

AgOTf

72 h

96% (48 : 52)

AgOTf

72 h

95% (54 : 46)

F
3

F

F

HgCl (91)F

F
a Combined yield of isolated 63 and 62.
b Determined by 1H NMR spectroscopy and HPLC analysis.

m®h­u_|&Qc(t&®.B7<@FR¯.B7<@F®3 Kn 2 ©c[(\LW«N;+/@13G®I~O©cªg]Vde¤¬wpV[

&.31) H®h­u_$'&*4=F3F#%!9)F5BEGB1Xl
Fig. 5. ®©c}v^/@13G&

13

a





$'&®J§pj­®*

9+98/'6JI>^LW*921):E%1):E

".32)

Hey-Hawkins, E. et al 2011)

Z (Å)
Y (Å)

Benzene79 Å3

X (Å)

H

H

Adamantane
136 Å3
H

H

H
H: Carbon(製造規制)o -Carborane (92) m -Carborane (93) p -Carborane (94)m-Carborane
143 Å33  2   !"(C2B10H12)
 

Fig. 5 *9257:EG]@K,&.]^bPk

MXoH= p-*957:94flBn#!o<RFe o-*957:92 m-*957:93$`*925719JEZm 95  64 $0-&:

Fig. 6p

HgCl

HgCl

H

H
95

64

Fig. 6 U0-&:*9257:ZmJ o92  93  t-4/98/'6t-BuLi$\Cm>^"%1):E 95  64 jf$iScheme 14p

N!#o2 *9257:dS

oJEZocb 95  64 

# 96  97 ;_Q]p_Q

96  97 ! 95  64 jf$ioDYbV[$g?



GQ$haoJEZm$`jf$TO

o3(19ZmJ$A`

14



p
p

Scheme 14 HAXs_"6,158XsHmj

H

t-BuLi (1.1 eq)
THF, 0 °C, 1 hH

then
HgCl2 (2 eq)

92

H

H

HgCl

then
HgCl2 (2 eq)

H
H 96

55%

trace

95

H
HgCl

H

+

Hg

60%

97

v.!*6XsAD\4

c[?

93

+

Hg

t-BuLi (1.1 eq)
THF, 0 °C, 1 h



 C

H

H

trace

64

fXsABOphbw;v1925 KvWhitmore v$77062:vo--)7#%.!
*6HAXs984c[?

Scheme 15.33)

bknvs 102  103 DQwQV[?

 o-49).!+96101^Q

GEo-vm-"6158.!*6HAXv.!*6Fti 95  64 mjaRv&$773(8:v0 °Cv2 MrHA4

c 102  103 v49)/8'8^Q<va` 95  64 @]`^Q

k=

wN 95  64 vdTPu>IWoYJvLq X edTWolU

Fig. 7w

Scheme 15 .!*6XsH_SgZ
Whitmore, F. C. and Hanson, E. R. (1925)
OH
HgCl

I2
(2.0 eq)OHo-Carborane
(92)

IHgCl

+

I

HgCl

CHCl3
98

OH

I2
99

t-BuLi (1.1 eq)
THF, 0 °C, 1 h
then
PhHgCl (1.5 eq)

100

I

HgX2

+

X = Cl and/or I
63%

ICl (2 eq)

Hg
H

OH

101

HgCl

+
102

15

CH2Cl20 °C, 1 hH
95
36% (2 steps)

It-BuLi (1.1 eq)
m-Carborane THF, 0 °C, 1 h
(93)
then
PhHgCl (1.5 eq)

ICl (2 eq) H

Hg

H

H

Cl

64
56% (2 steps)

HgCl

Hg

Cl
Hg

H
64

95

Fig. 7 95 

I+

CH2Cl20 °C, 1 h

103

HgCl

HgCl

64

16

X

l?m -;5794;b|sR*g+:;zXj 1,3-/,<eHKU}i l@mx%, -;574;b|P 95, 64 *ur
< 61 *OvKUV*aw*gKU*q 61 *NL*D`t&, 1,3-/,

Table 2!Entryk%95 "

24 [~KU#eHKUyqIZ'o_

95  AgOTf *cVHF

Entry 2\]AKUV>Q

B 63  62  97:3 afW




dG

KU

40 EKU[~eHm--;79<h^ 64  AgOTf *gKU

SCzXV 63 fWEntry 3!64  AgOTf n"M)*g(4 mol%sR{#T{jzXj 63 fW')

Table 2 -;5794;b|P]A`t

Hg-reagent
NHTs
61

Additive
CH2Cl2, rt

+

N
Ts
63

N
Ts
62

Entry

Hg-reagent (mol%)

Addtive (mol%)Time

Yielda (63 : 62)

1

HgCl

-

24 h

0% (>99%)b2

95
H (5 mol%)

AgOTf (5)40 min94% (97 : 3)c

AgOTf (5)40 min>99% (>99 : —)d

H

HgCl

3

64
(5 mol%)464 (4 mol%)

AgOTf (4)70 min>99% (>99 : —)d5

64 (3 mol%)

AgOTf (3)5.5 h98% (>99 : —)d6-

AgOTf (5)24 h

0% (95%)b

a Combined yield of isolated 63 and 62. b Recovery yield of61.

c Determined by 1H NMR spectroscopy. d Determined by HPLC analysis.

Entry 1, 2 J 6 o_&-;5794;PHb| 95 $ 64  AgOTf P821.0KU%-;5794;b|3:69=3QY

17('

sRp*i

W

lC

r

zNxj96 61 gZYn4~oA

qK

Fig. 8

|TRid104 L_uF
|Tj`R=

]



H

AgOTf

HgCl

64

HgOTf

H

AgCl
塩メタセシス反応

104

HOTf

104

NHTs

61

N
Ts

TfOHg

-OTf

N
Ts

Hg

Hg

63

107

106

105

+

Fig. 8 uF`Rm?QUJ]\ ^Ey3sRkw
3&.(1EX

5eR=Abe=?Q

Entry 11,3-;P&#2M8hR7E:Z = 4:1B 108b @c>3 109b fS
XTable)%1!-* 108a ?Q4~oAI:6p|TR 109a JjfS

+1E

[v

Entry 27 6.(1E," 108c  108d 4~oA6p|TR;)/2'|Tj

e=?Q{tUJ?Q]\

Entries 3, 4)/2'|Tje=?QFig. 9l7 6pVEa<GjHJ#$)0!1}O

112  5-endo-trig De=?Q{tq

18



9S,P>DQC-N N5+.7H25G

Table 3

H

HgCl

64
(4 mol%)AgOTf (4 mol%)

NHTs

+

CH2Cl2, rt

108

Entry

N
Ts

N
Ts

109 (Allyl)

110 (Vinylene)

108

Time/Yielda

109

NHTs

10 min

108a

>99%

N
Ts
109a

(Ally:Vinylene)b

110(>99 : —)

N
Ts
110a

(>99 : —)

N
Ts
110b

1

(E:Z = 4:1)

2
NHTs

30 min

108b

94%

N
Ts
109b

NHTs

15 min

N
Ts

108c

95%

109c

NHTs

15 min

108d

94%

3

4
Ph

Ph

N
Ts

(>99 : —)

N
Ts

110c

Ph

(>99 : —)

109d

N
Ts
110d

a Isolated yield of 109d. b Determined by NOE assignment.

R
7

H Ts
N

R 7 H Ts
N

H

R

NTs
R

H

111

113

112

N
Ts
(2,5-trans)

Fig. 9 L0T@>O;

 FW1H>25G4=>KR#")*8H20 116a I?
<V 2,4,6-!'&

Table 4X3M 114a 4=W

Entry1X($"((%"(9Mts 9:B

Entry 2XC4=W4=>/19

W!(9114b JWEntry 1 6EYAU

#

3-,

3

115b 2&,



+%

4



* 115c3115d "

Table 4 !1/$Mts !' 114c  114d Entries 3, 44(0 C-N .*)
H

HgCl

64
(4 mol%)AgOTf (4 mol%)

NH
PG

114

1

NH
O
S
O

2

PG
116 (Vinylene)

115 (Allyl)

Time/Yielda

115

N
S

1h
>99%

(Ts基)

N

PG

114
Entry

+

N

CH2Cl2, rt

O
O

114a

115a

NH
O
S
O

N
S

1h
98%

O
O

(Ally:Vinylene)

116

N
S

+

( 91 : 9 )b

116a

N
+

O
O

S

O
O

(Mts基)
114b

3

NH
Mts

5 min
>99%

114c

115b

(>99 : — )

116b

N
Mts

+

N
Mts

115c

(>99 : — )116c(E:Z = 10:1)

4

NH
Mts

N
Mts

1h
97%

114d

115d

+

(>99 : — )

N
Mts
116d

a Combined yield of isolated 115 and 116. b Determined by 1H NMR spectroscopy.

20 >L',(N"*5K

?E?EF36;4A029ITable 5MEntry 1 D!',(<

"&#$)*4A0. 119a B;CJ
A0.8

 117a L%L117b  117c 1-'(4Entries 2, 3M Table 5 5K-G:=HC-C F3+',(+1,3-/7"*03@

H

X

HgCl

X

64
(4 mol%)AgOTf (4 mol%)

X

OMe

+

OMe

OMe

CH2Cl2, rt
MeO

Entry

117

1

MeO

117a

5 min
>99%

CO2Me

MeO

118

118

Time/Yielda

OMe

MeO2C

MeO

117

MeO2C

119

(Ally:Vinylene)

+

OMe
MeO

119

OMe
MeO

( 93 : 7 )b

118a

CO2Me

MeO2C

119a

CO2Me

+

2

OMe
MeO

1h
97%
MeO

117b

TsN
3

OMe
118b

OMe
( >99 : — )

TsN

OMe
MeO

30 min
98%

119b

TsN

OMe

+

MeO

117c

MeO

OMe
MeO

118c

( >99 : — )119ca Combined yield of isolated 118 and 119. b Determined by 1H NMR spectroscopy.

21

K.L 4;
 >J

\!"/Y:E%6 1,3-#B)*8[D+O

\<T@Z1VR
2?$FI

"

] XG

"1)@Z(S\>' AgOTf C

]>*8?$ 1,3-%6#0W

ANANP-59*8&C,Q

ANHNP-59*8\!"/Y:EB)*8

M3-9

8C=7]H

H t-BuLi (1.1 eq)
THF, 0 °C, 1 h

m-Carborane
(93)

H

then
PhHgCl (1.5 eq)

HgCl

ICl (2 eq) H

Hg

CH2Cl20 °C, 1 h103

64

56% (2 steps)



Cl
Hg

64 (4 mol%)
AgOTf (4 mol%)

NHTs
61

CH2Cl2, rt
70 min

N
Ts
>99%

63

64 (4 mol%)
AgOTf (4 mol%)

NH
Mts
114b

MeO2C

CH2Cl2, rt
98%
1h

N
Mts
115b

CO2Me

MeO2C

CO2Me

64 (4 mol%)
AgOTf (4 mol%)

OMe
MeO

OMe

CH2Cl2, rt
97%
1h

MeO

117b

118b

A Carbaboranylmercuric Salt Catalyzed Reaction; Highly Regioselective Cycloisomerization of 1,3-Dienes
Yamamoto, H.; Sasaki, I.; Shiomi, S.; Yamasaki, N.; Imagawa, H. Org. Lett., 2012, 14, 2266–2269.


22

U

ÄUÃ FK6N25O¢¦w1L@EJ?L«Ü=KCJQ=Ý¸     ÄRÅ Ó 01'1()!%a

+8 t (+1900 t)&

3'1$b -︎ '#1
3+&

2"&

1





/

*

()!%c

...+++++++++++++++4+Os, Ir, Ru …12 ,+().4.Pt … 31 t .
4+Pd … 64 ,++4+Au … 297 t+72 t
a2013.b  2017c 2016)«ÜÞâÑÚÈ 8 t !(åt`µ£¨).34) å 28 åt×È«^È«Ü®§«ÜÖb_&ÌË

keÀ©).22) Û'åYåÛ

å}«ÜÐp%«Ü,d¶µ£DN98å«Üz+)Z¬Ý¸%«Ü,h±º³)#68<I¥ÆiÔã)æ

 Rå¹ÛOs, Ru, Rh, Pd, Pt, Ir%Û
)Ò|Ï

ä

'åx¿½Â

äÛåj~l'DN98"d¶*).35) å*'Ûä](å08H?/Ißª$yo*)#å*"rm%ad¶ß+)Û³68<IÝ¸§j~cÙå¯X½ÂÎÁ¤ºÝ*.

årmPad¶nÏSvRÇlf,Ý¸)åcÙ,°)æ\å W{~¡'åª¸ärmsáqØj08H?/IOsO4,FK8;MOÉG.3N1D
9L_ Mc-OsO4121Ý¸g)Scheme 16.36) 121 qØj08
H?/I

Ò|)-L4O70QLjl­¸d¶*å²uÕ*)æ"å{à{~Û·'å´[¾ÊÍTc)B>N26-A:.=
HAP

Û.0OVÏ,)¼»å3 ]L<?/I,
23

Ru-HAP 124#x.37) wU124 $A.EA#tQ
FYne!*@ECGV"!fHAP jkW`Ys

9?0&>, 85,A, Pt-Mo SjkhP!.38)
Scheme 16 

Os
Kobayashi, S. et al (1998)
MC-OsO4 121

OH
OsO4

H2O, Acetone,
CH3CN, rt, 12 h

120

OH
122

ポリスチレン素材
マイクロカプセル

Microcapsule (MC)-OsO4 121

Recovery of 121 >99%
Ru
Kaneda, K. et al (2000)

H

O2 (1 atm)
Ru-HAP 124

OH
OH
123

CH2Cl2
70 °C

H

OH

P
O

O
125

81%

O

H

O Ru OO POO nRu-Hydroxyapatite (HAP) 124
Au, PtPd

Kobayashi, S. et al (2007): PI-Au 126
Kobayashi, S. et al (2008): PI-Pt 127
Kaneda, K. et al (2015): Pt-Mo/HAP 128

Uozumi, Y. et al (1999): Pd-PEP 129
Kobayashi, S. et al (2003): PI-Pd 130
Kaneda, M. et al (2005): Pd-HAP 131

Polystylene
O Au
HO
HO
Au O

Ph
Au O

Au

P

OH
OH
O Au

O

Ph

H
N
n

O

Polystylene
Polymer-Incarcerated (PI)-Au 126

Cl
Pd

PEG-PS resin-supported Palladium-Phosphine Complex(Pd-PEP 129)JScheme 16 TH}qIX[_r!OZ)A3?C7

Polymer-IncarceratedWyYPI-Au39)126 OZ~[|iK



=@(4BC+@.EA–=@14BC+?;6NSMB0C:E2PEPjkW
9?0&><1;%CMPd-PEP 40)129 Fmuc|^apDLo

x

"!.

b

 Slica Bond Pheny®

132#Rl/@)-AjkW;'8Au6@;?E6SiPh-HgOTf134"!Scheme 17.30b) 134 uxv\] sp3σ S#dh!g{z24JE4<@jFvb?7L6q|P"bhw)153*0,-1
5%;U#k^mDZA#
be$


#

!

CK%]!
l



o}$#.41) e$=bsTYbO#6DZM0.10.2%pX#

c=#

gR佐々木

博士論文 (2012)

Hg(OAc)2
Microwave

Si

AcOH
140 °C, 1 h

Si

HgOAc

HgOTf

2) WashSiPh-HgOTf 134

133(Hg-loading: 0.2 mmol/g): シリカゲルn-C4H9SiPh-HgOTf 134(20 mol%)
CH2Cl2rt, 20 min

NHTs

N
Ts

>99%

135
Recovery of 134 >99.9%

1) TfOH
Si

Silica Bond ®
Phenyl (132)



t

シラフェニル水銀トリフラートの調製と反応例

Si



$ "QR[u9[:$7L6qbDZA

Scheme 17
郁雄`V

n-C4H9136(Hg leaching 0.091%)

t134 a#/'.2bBGfDZ#\i~_%y~_8xIdNH%z.42) 1958 W, Dessy !+&2(2b+/'.2bQR[%o}#nmOBbr%j 137a-d
>{S%y#Scheme 18
Scheme 18 



Dessy, E. D. et al (1958)
R Hg R

Hg

酸との反応性（相対分解速度）HCl

137

DMSO/Dioxane>

Hg

R HgCl

+ HR

>>

Hg

>

Me Hg Me

137a

137b

137c

137d

170

100

1

0.2


25

)/&,9g 137b )$*0:.9g 137c 
H

"

#TO!.

h" 1 B 100 Dn#{x SiPh-HgOTf g#rFig. 10C138 jIK^}UM\u@lk HOTf  139A AwM

0:+;I

5,%6$'; 140A #v 136 k`Nb SiPh-HgOTf

Fk

Pass B pg384<#de/&,9S
0:+;Iy_"$"!Pass A>= HOTf"UM140B  141 #vu@gV

h"GL



Si

Ph

Pass ATfOHg

n-C4H9

Si

Si

Ph

Ph
HOTf

Hg

NHTs
138

139A

+

N
Ts

n-C4H9136

Hg(OTf)2

Si
Si

TfOH
Hg
n-C4H9N
Ts
139B

n-C4H9

N
Ts

140A

Si

Pass B

HgOTf

–OTf

Hg

n-C4H9

N
Ts

Si

H

+

Hg

–OTf

OTf
Hg

N
Ts

n-C4H9
NBulkyTs

n-C4H9141

140B

Fig. 10 

 gh"JQ B}mb{xt=sl(9-27,9gVXY_]zP#at=s 1516 1<)p(927,9gV(9-27,9/&,9g 102  103 /&,9S#~ 95  64 #c[q(9-27;g
E


o

"

"134 

~IMi(9-27;g#de?R=u|#gh"ZWfy!Ly_

26



v;w '4-13,4PFio\su 

'4-13,4iPy\{%_@e0&,4PFi

90'4-13,4PFi 64 %##)(552+6n HOTf %kE"CY%h

FS

MPi%rH[gl%Ap"gl9K#" 90  64 %## 1H-NMR V

Fig. 11|Lj0&,4PFi HOTf kEJbCQ!120 bZ
U?C#8a, 64 =#yTVRO\%tb120 b HOTf c"$

100

93
90
HgCl

Recovery (%)

80
60

HgCl

H

90

64

64
40
20
0 0
0612 24

20

48

40

60

72

96

80

100





120

Time (h)
水銀試薬 + HOTf (1 eq), 食塩水で処理，1H-NMRで標準試薬(CHBr3)を用いて定量測定

Fig. 11  HOTf %kE

 0&,4PFi

Co%JVHPLC-ICP-MS %mV

 64  90 CYW"}S`z*6+7X>qxd90 H[gl

HgOTf2 J8/7(.+76eB

GD

fN HgCl2 #Fig. 12!90 :]! HOTf Ph-Hg xI~ HgOTf2  HgCl2 ;<iPC #^
m

#"

27









CPS (x107)

HgCl

H

10

PhHgCl+TfOH
Decomposed
material of PhHgCl64

8

PhHgCl

Hg2+

HgCl
2
Mecury (ii)chloride6

MecuryHg(OTf)trifrate 2

4

m-Carbaboranyl
HgCl
HgCl

m-Carbaboranyl

PhHgClPhHgCl

2

0
0

50

HgCl

100

150

HOTf

200

250

HgCl
+

H OTf
90

142A

300

350

-OTf
HgCl

NaCl aq

Time (s)

400

C6H 6

H

HgCl2

+

NaOTf

142B

Fig. 12 NFY4WS 93 2:DG HPLC-ICP-MS VA )@\64 -TUJ5>79*,J;<E<MX"RCQ

Table 6 !($%'#(4/FY&


\&

"8

]PB\64 HIL=+ZK 300 mg/kg

O3=+\0?&



1.







"=+



Table 6];<E<6[

a) 投与量に対するマウスの生存数

経口投与 n = 5)

Day 0

Day 2

Day 4

Day 6

Day 8

Day 10Day 12

Day 14

Vehicle

5

5

5

5

5

5

5

5

50 mg/kg

5

5

5

5

5

5

5

5

100 mg/kg

5

5

5

5

5

5

5

5

150 mg/kg

5

5

4

4

4

4

4

4

300 mg/kg

5

5

3

3

3

3

3

3

28

g64  LD50 KCT 300 mg/kg 30^abg64 N4OF;=RX[OF6

gJWQe@PFig. 13.43) g64 )$,Qe_D!.44)

 



HgCl

H

64

(1) HgCl2

LD50 = 6.0 mg/kg(2) PhHgOAc(3) PhHgCl

LD50 = 13.3 mg/kg
LD50 = 60.0 mg/kg(4) MeHgCl

LD50 = 58.0 mg/kg

LD50 = ≥300 mg/kg(MeHgCl < 0.76 mg/kg)

Fig. 13 YQe@

0c\LOFPb

g#,%&*-1>/Z'+(.Qe"d\]2F"758A

B6F9Hg 64 "?U1>/Z<E:fSV

GFig. 14h




固

HgCl
n

安全な水銀試薬C-Hg結合の高い安定性(水銀漏出のリスク回避)Fig. 14 I1>/ZQe<E:M`

29

t>u 48):'(;cdR&9.37-9
f+807<+ p =xq&9.37;Fig. 15 sK2 ZTS"m*#-%;

o#9'9D"eqWE

"Gm





Nw.32)

M\]@Q=v|y}{"|

H

H1) n-BuLi(2 eq)

2) R1-I

R2

R13) R2-I

THF–78 °C93

R1, R2 = alkyl

143

144

Fig. 15 &9.37;8;&<WEg

FCq_g Scheme 19 s93 " 2 Z t-BuLi "m*#-%;K

8;&<+85+'))896<,1:/; HgCl2 "HgCl2 kI5 mM YbBz

145 "}{

Scheme 14 s

*&9.37; 96, 97 rZJ145 !
L





AKCl^"aXn

146 W

~H AgOTf "+9$;hj







[AgOTf "mi]K

+807<+C 147 

Scheme 19 @Q=vfT}{

H

H

93

1) t-BuLi (2.0 eq)
THF, –78 °C, 30 min(MeO)3Si

2) (MeO)3SiC3H6I (1.0 eq)
0 °C, 10 min
then HgCl2 (3.0 eq)–78 °C, 5 min
HgCl

ポリシロキサン

146

H+

HgCl
3

145

EtOH
reflux, 5 day

AgOTf (2 eq)
rt, 20 min
thenwashed withtoluene3015 2<*1:+;UP?V`O

"mO

kI



HgOTf

147

Fig. 16 q$l?

 146 $p

AcOHTFA, HOTf a pvBhyh+.,1MS"!2YE$l+.,1;

uFh+.,1MS"!

 146  b p$^|!

#_\52 mol/L EGC3400 rpm WU`nD2RuL9J$p 146 P"!
6a;<F@77Ld

bTVi$t8

KDuFN 2.28 μm t8:gf!

#{ 146 

4.29 mmol/g cI



 
The number of 144

Hg loading; 4.29 mmol/g: 2.28 μma) AcOH, TFA, HOTf 使用時b) 2 M HCl aq 使用時

 (μm)

c) ポリマーの粒子分布 (光学顕微鏡で実測)

Fig. 16 4D2w&/)*-(/bE 146

O147 eR; 4D2w}z20 mol%$ls2r m  1,3'%0 117a  118a j;=Q$^|~Scheme 20 

118a kSo!5 ZWU=QHx50%[=Q<X 117a $A>!x]

Scheme 20 4D2wbE 147 =QR^|

147(20 mol %)
OMe
MeO

117a

OMe

CH2Cl2rt, 5 day

MeO
118a
35%
(Recovery of 117a 50%)
Recovery of 147 99.999%aa 還元気化原子吸光光度法で測定

31

 <x

kW

}:L}4G2jsoup"sScheme 21~85_}()-$)%&&-0TEOS">
rKT}+.,1I`M?7}BOIv

@;BOg{"d64G2jsoup"aS

Scheme 21 ()-$)%&&-0TEOS"\>H1) t-BuLi (2.0 eq)
THF, –78 °C, 30 minHsoup(MeO)3Si

2) (MeO)3SiC3H6I (1.0 eq)
0 °C, 10 min
then HgCl2 (3.0 eq)–78 °C, 5 min

96

HgCl

O
O

Si

O

O

O

O Si

O Si

Si O

O

Si O

2 M HCl aq
TEOS (n eq)

3

EtOH
reflux, 5 day

145

OEt
EtO Si OEt
OEt
TEOS

反応空間を有するポリシロキサン

Si

.45)

O

Si

AgOTf (2 eq)
rt, 20 min
HgCl

ClHg

HgOTf
P

then
washed withtoluene

66

HgCl

P

: ポリシロキサン

148

7DcflY9A=
p

}



}TEOS " 3 Nz

BOP"dt

TEOS " 5 Nz\>Table 7~kW+.,1rK"^mFZbq

 20 Nz[CUnJBOP"e





!

}Entry 2 e


!

~

32

E3

}117a



~}V}i2h 21 *1' 64/AgOTf BOXw

4G2jrK 66 "^BO#./HyRP
yR_]Q

+.,1"u} 118a |

Table 7  TEOS mIbJ

HgOTf
P

66

OMe
MeO

OMe

(20 mol %)CH2Cl2, rt

117a

MeO

Hg-Loadinga(mmol/g)Time (h)Product (%)b(118a:119a)c

1

3

2.30

14

60 (>99 : –)>99.999

2

5

2.22

12

94 (>99 : –)>99.999

3

10

0.97

13

88 (>99 : –)99.999

4

20

0.74

15

87 (>99 : –)99.999TMsQY 3.27 μm 

Recovery (%)a of 66

b Isolated yield. c Determined by 1H NMR spectroscopy.

8<,>(+?eiN'=47;2=j1<6;@1 66 #bBMAt{PR

66 sUHS Fig. 17 

~fNQ[#p8<9@y%3=)@HaN X wHFkEDX148 l]JZ 66

sQv^#zd^EuFig. 18AgOTf l]J60u5@*

K\OTf C_
q}

119a

TEOS (eq)!g|5 W TEOS #mI

#`X

MeO

Entry

a還元帰化原子吸光光度法で測定

r

118a

OMe

!

x

V!

gG

 66 1<6;@1Dh!148 Ou$&?

#rL



czd"Ou

O:/.,-K\on]OJ

33

O:/.,-gG!



 (SiCB-HgOTf)
HgOTf

P

TEOS (5 )

Hg loading = 2.22 mmol/g 

66





3.27μm
10 µm

(μm)

Fig. 17 66 

!SEM

活性化前

活性化後
HgCl

HgOTf

P

P

+ AgCl
148

Fig. 18 148  66 

66 X EDX

34

`Aa 6B5b>KDl5fL TsVp)/-.4)hG>K

!6B5bhG 66 W\L$^ksXc-Xcd@IM>K!%/403('2Z=>KQi`5_>KL$^k 117bs117c $s117d $DltTable 8.

&2*40 Friedel-Crafts CZ=>K$jEntries 1-3tdPs"Dl
/0CnN] 118bs118c, 118d gF?Y[M('2$md 117e t5Os%/403'23

[@Mr8SR!EoZ=>Ks7od@9e$H;<J!

q

6:1 U[M!

#Entry 4ts%/0CZ=: 118e ,+12CZ=: 119e 

Table 8 Dl5fLQi1,3-('2Z=>KsC-C d@

HgOTf
P

X

X

X

66

(20 mol %)
OMe
MeO

MeO

120

MeO2C

OMe

CH2Cl2, rt

117

Entry

MeO

CO2Me

MeO2C

24 h

MeO

117b

( >99 : — )118b>99.999%

117c

OMe

86%
MeO

35

MeO

119b

TsN

14 h

MeO

OMe

TsN

OMe

CO2Me

OMe

TsN
2

119

+

88%
>99.999%

MeO

OMe

Product (118 : 119)c

MeO2C

OMe

+

118

Time/Yielda/
Recovery of 66b

CO2Me

1

%

+

( >99 : — )
118c

OMe
MeO

119c

15 h

3

NTs
117d

MeO

+

NTs

92%
>99.999%

119d

118d

OMe

MeO

OMe

38 h

4

MeO

OMe

+

67%
(E :Z = 5:1)

NTs

( >99 : — )

(6:1)

H

>99.999%

H

118e

117e

119e

a Combined yield of isolated 118 and 119. b還元気化原子吸光光度法で測定
c Determined by 1H NMR spectroscopy.

 5D7$%/4?
/)7$#C&6


99.999%"!:@Table 9E3%/

CB2981

E%/.>,(&6=+E


Table 9 *A<04?1,3-7$%/DC-N ;'

HgOTf
P

66
n

NHPG

n

(20 mol %)NPG
n = 0: 63, 109
n = 1: 115

CH2Cl2, rt

n = 0: 61, 108
n = 1: 114

Entry

Substrate

Time/Yielda/
Recovery of 66b

NHTs
61

>99.999%

NHMts

90%

108e

>99.999%+NPG
n = 0: 62, 110
n = 1: 116

+

N
Ts

93%

(>99 : —)
63

18 h

2

n

Product

24 h

1

N
Mts
109e

36

D-

N
Ts
62

+

(>99 : —)

N
Mts
110e

D

24 h

3
NHMts

96%

N
Mts

114b

>99.999%

115b+(>99 : — )

116b

19 h

4

NH
Mts
114c

+

N
Mts

85%
>99.999%(>99 : — )

115c

NH
Ts
114e

+

N

92%

Ts

>99.999%

N
Mts
116c

29 h

5

N
Mts

N

(>99 : — )

115e

Ts
116e

a Isolated yield. b還元気化原子吸光光度法で測定%8

1+ 16) 10.

Entries 5-7 2Friedel-Crafts $1;+!06'#!0":;(+

4&

+

Table 10 %83,-71

+,2

Table/9.*5

1)





<

+

HgOTf
P

66
n

n

(20 mol %)
OH

NuH

Nu
CH2Cl265, 149
Entry

67, 150

Time/Temp./Yielda

Substrate

Recovery (%)
of 66b

Product

8 h, rt

1

OH

NHTs

65

OH
2
NHTs

149a

>99.999

N
Ts

>99%

67

16 h, rt>99.999
Ts

83%

150a

10 h, rt
3

NHTs

OH

93%

>99.999

N
Ts
150b

149b

37

24 h, rt

4

NHTs

OH
149c

71%

150c

OH

5

>99.999NTs

6 h, reflux

MeO>99.999

MeO

70%

149d

150d

OMe

OMe

OH

6

OH

+
(8 : 1)

70%

149e

MeO

7

12 h, reflux

MeO

OMe
1502

150e1

18 h, reflux

TsN>99.999

TsN

78%

149f

>99.999

150f
a Isolated yield. b 還元気化原子吸光光度法で測定





?<
11. 

"



C3=



!$+A49-89:'.2%0 46) (B*>C-0

C66 ,@7)&

625/



Table

Table 11 *>#;13=$+A C-N :'.2%0

HgOTf
P

OH
R1
151

Entry

1

2

O O
(20 mol %)
+
S
152:
R
=
p-Tol
H
N
R
R2
2
3
CH2Cl2, rt
153: R = OMe

Substrate

OH

66

O
R3

O
S

NH

R1

Product/Yield/TimeNHSO2R3

151a

38

154: R = p-Tol
R2 155: R = OMe

Recovery (%)
of 66b154a: 92%, 6 h(R = p-Tol)>99.999

155a: 87%, 5 h(R = OMe)>99.999

3

NHSO2R3

HO

4

151b

5

HO
NHSO2R3

6

151c

7

NHSO2R3

OH
Ph

Ph
8

151d

154b: 97%, 26 h
(R = p-Tol)>99.999

155b: 92%, 16 h
(R = OMe)>99.999

154c: 78%, 3 h(R = p-Tol)>99.999

155c: 70%, 0.5 h(R = OMe)>99.999

154d: 90%, 7 h(R = p-Tol)>99.999

155d: 79%, 6 h(R = OMe)>99.999a Isolated yield. b 還元気化原子吸光光度法で測定*"&*&)+ 156 I56? 30b) ;XL!+%,* 157JAScheme 22.
Scheme 22

*"+R:I56?2K

HgOTf
P

n-C4H9NHTs
156(20 mol%)

66
CH2Cl2, rt, 1.5 h
99%
Recovery of 66>99.999%

 -W]GY$)'(,$R:6?




N
Ts

n-C4H9157

.CTPDK@MU]F]R:12K4HES^3W

)*

*#,

* 650.5 mmol=]20 mol% 66 KOV<\Q^
 Table 12 N]R:12K

6?B[>Z08

I5/ 67 ;XLJA]66 ;XL97

39

^

]

Table 12 '<4D(!"7!6.#3A
66(20 mol%)
OH

NHTs

N
Ts

CH2Cl2, rt

65

67

Run

1 st

2 nd

3 rd

4 th

5 th

6 th

Yielda

>99%

>99%

>99%

>99%

>99%

>99%

Recoverb>99.999% >99.999%>99.999%>99.999%>99.999%>99.999%

2.5 h

2.5 h

4h

5h

2.5 h

Time

2.5 h

Cleaning andReactivation
....c

15 th

16 th

17 th

18 th

19 th

20 th

....

>99%

>99%

>99%

>99%

>99%

>99%

....

99.999%>99.999%>99.999%>99.999%>99.999%>99.999%

....

12 h

12 h

12 h

16 h

24 h

48 h

a Isolated yield. b 還元気化原子吸光光度法で測定 c Run 7th, 6.5 h, >99%, >99.999%; Run 8th, 6.5 h, >99%,>99.999%; Run 9th, 7 h, >99%, >99.999%; Run 10th, 7.5 h, >99%, >99.999%; Run 11th, 7.5 h, >99%,>99.999%; Run 12th, 8 h, >99%, >99.999%; Run 13th, 9 h, >99%, >99.999%; Run 14th, 10 h, >99%, >99.999%.

20 &8!"7G$-*= 48 2E,?
G

766 (CG1 10/$-2E,?
6.#

H 

GFig. 19 ;GAgOTf !6.#G48 2Eの@) 66 G21 &8$- 3 2E9>

66 7 3 &$-:B

HgOTf
P

66

Reactivation

G%F

AgOTf
rt, 20 min

7

Cleaning

2 M HCl aq
rt, 1 day

HgCl
P

148

Fig. 19  !"740

6.#5よH+G再た．

      b-c DL Rap (#%&"(Un>YK^`hmC

ABpTK0Un6:Y,=+d7J5 66 lkgUnj@



EF

i3

q

pR54[

q66 S3o\Un<8Z_;N

pM]Un!'$&*!d7J?
j@gIWp (#%&"(Un>

/OqpVX)2WK69gp.HpHgOTf2 OP[ef1[9
4[



QG

q

HgOTf

Si

66
ポリシロキサン

高い回収率

再活性化可能ポリシロキサン架橋型水銀塩

安全性; LD50 (マウス) = >300 mg/kg

HgOTf
P

OH
NHTs
65

P

: ポリシロキサン(20 mol%)
66
N
Ts
67

CH2Cl2, rt
99%
Recovery of 66 >99.999%

5 th
99%
4h

1 st
99%
2.5 h
66の
再利用

再活性化
2 M HCl
AgOTf
20 th
99%
48 h

A heterogeneous mercury salt catalyst stabilized by m-carbaborane
Yamamoto, H.; Yamasaki, N.; Hamauchi, H.; Shiomi, S.; Sasaki, I.; Seyama, K.; Mima, Y.; Nakano, 
M.; Kawakami, T.; Miyataka, H.; Kasai, Y.Imagawa, H. RSC Adv., 2015, 5, 94737−94742. 

41  r:q Myers QEowtKMan      r9s [| 1996 ZMyers N--(5/,3)7NBSH159"l#45#5'85
158 ?uOmbK"A#5&7 161 YScheme 23.47) –30 °C Ck<F]Madk

, -(5RNs Rw

fMa>D 160
2006 ZMovassaghi nEowtKMa"SP 160 "^0 °C @;

wptKMa}ho~x=UVLXk\'7+685

NBSH $*1605$27{YD

Ma

yj

!



IPNBSH 162".7,47%WeEowtKMa"Nv.48) 

IPNBSH "jgI#45/,3), 163 UV163 $27B"JiGzwptKMa

~x

Ma

k\"LXH_`yya$*1605$27"JiGz#5&7Tc



`



Scheme 23 -(5/,3)7"l Myers QEowtKMa 
Myers, A. G.; Movassaghi, M. et al (1996)

OH
R1

R2
158

DEAD
Ph3P

O2N
H
+
N
H2N
S
O O

–30 °C

(Ns基)

H 2N

– ArSO2H
– N2

NNs

R1

R2

NBSH (159)

R1

≥ 0°C

160
(unstable)

H
R2
161

Movassaghi, M. et al (2006)

+

158

N

H
N

DEAD
Ph3P
Ns

THF, 0 °C

IPNBSH (162)N
R1

TFE/H2O

NNs

163(stable)161

Deprotectoin

R2

H+
weak H+
N

N

Ns
R2

R1
163

H 2O
Acetone

H 2N
R1

O O
S
N

NO2
H

R2
164

ArSO2H

42

N2

1

R1

N

H

N
R2

5

165

R1

R2
161

 Myers  Movassaghi nEox

–-Acylfulvene167GNaJmtLM_!–-Tetracycline166
gm`!XFig.

20.49, 48a) f{B=UTrauner ':>5hM_!3.%&":%;#1+-Lyserigic acid169Caribenol A172jNaJmNaxrtL

.50)"9:418*1ACF]z!

m418*1kiK"9:":(>:kivcM_|

VM_

"9:418*1|Myers, A. G. et al (2005)

Movassaghi, M. et al (2006)

D

Fuji, N.; Ohno, H. et al (2011)
HO2C

O

N

HO



N

OH

H

NH2
O
OH O HO H O

RO

R = H; (–)-Acylfulvene (167)
R = OH; (–)-Irofulven (168)(–)-Tetracycline (166)

NH(+)-Lyserigic acid (169)

Trauner, D. et al (2017)
IPNBSH
DEAD
Ph3P

H

HO

then
HFIP, H2O

O
170

H

H
H
O

O

Caribenol A (172)171

Fig. 20 Myers QEox

O

tLM_!mNapq

 ?eywb[ pqYHgOTf2 V!m"9:":(>: 151 +:6<"71 152153 IWlt-rtuN^aM_ 46) !SPEq. 1,

Scheme 24. 2012 \, "9:":(>:!"9:)9:$>/:Tc
+:6<"71skiKM_`O@!}HTBDPS R!g"9:)9:$>/: 177  N,N-",-:0):418*<178d~"9:"72LM_Z

Eq. 2.51)

43

Scheme 24 Rk&-*,0&dG:Hl"-."+(=>M

Yamamoto, H. et al (2011)
O O
S
H 2N
R3

OH
R1

R2

+

H 2N R 3

TfOH

OH

HN

HO
R2

R1

173

NH

R1

…….

R1

174

R3

R2
HgOTf
175

(1)

R2 R3 = p-Tol: 154
R3 = OMe: 155

H
R3
HO+ HN

R3

R2
HgOTf

Hg(OTf)2

OS

R3

rt, 2 hR3 = p-Tol: 152
R3 = OMe: 153

151

R1

O

Hg(OTf)2(2 mol %)

-OTf

NH

R2
Hg(OTf)2

R1
176

Yamamoto, H. et al (2012)(Ac基)OTBDPS
R1

R2

+

H 2N

Ac

N

177

 a^qHg(OTf)2(2 mol%)OSO O

CH3NO2

(Ts基)

Ts
N

R2

178

NH

…….

(2)

R1
179

 HgOTf2 dG"-."+(=>M!]J1q;g Myers>M;p3$"%/ 165 EN?_"-.)',$'=@T!qRkD
dG>Mec

qOi6X`j[=>MMV

]r83XqScheme 25 YqN-Boc-N’-&#.)',$'6952)!SQ< 180 !ecLqj9U

 Boc B!`5f

`n7q165 !\W`Z[=>Mhb

181A o2"-.&#.)',$/ 181B

`Z[=>MqPKF

. 53)44

, &#.B]rImqhb4CA

Scheme 25 Myers 





Ts

N
H

H
N

OH
R1

R2



(Boc基)

O
Boc
N
H
NTs

O
69

Hg catalyst

R1

R2

151

H

H
N

N

Ts

1

– ArSO2H

H
R1

H

N

H

– ArSO2H
ref. 53

181B

45

– N2

N
R2

165

R2

R1

N

5

181A
Ts
N

– Boc

180

R2

R1

H+

H
R1

R2

161

k<l #4-/2+4]|tM dMyers Jy>fqznGR}e E-Undec-6-en-5-ol182a

GRKw

N`&$551'6:

N-Boc-N’-)%4.*2&* 69 1.5 O{!34!0,FGR
tMBjk<j}e
X~GRgf

vTable 13

9I8mtM 66 20 mol%
 183 

 10%

Q

d



<{F

 184 ;cSbEntry 1184  183 LUvEZfV_


24

s@



Table 13 9I8m]|tMdaninoHPSGR\u 
HgOTf
P

OR

+

n-C4H9n-C4H9
182

Entry

Ts

H
N

N
H

Boc

H
N

Boc

CH2Cl2, rt(1.5 eq)

69
Substrate
(OR)

66

NTs

n-C4H9n-C4H9183

Catalyst(mol%)

Time

Product (%)aRecovery (%)
of 66b1

OH 182a2024 h

10 (34)c>99

2

OTBDPS 182b

20

24 h

47 (12)d

>99

3

182b

20

48 h

45

>99

4

182b

40

24 h

43

>99

n-C4H9n-C4H9a Isolated yield.
b 66 was recoverd using a filter paper.

(E/Z mixture)c Isolated yield of homodimer 184.
d Recovered yield of 182.

O

n-C4H9n-C4H9184

 rpBlt.*2&6^[C 178
exhGRKw
Dc

EZfTA]zKdan-inoHPSGR}151b %34"7(4 186 LY




Ws@

TBDPS %34"7(4LY46

<{F= 185 

Fig. 21.51) GRKw 182a

 182b?\udGREntry2. TBDPS 2?@-C5@ 182b Tk¤)lWvHK¤l 183 U#Eq(LX¥$ 24 rTk# 12%So¤47%FgUZU)

&¤Entry 3 $4 %¤2 pTk$ 40 mol%a+#Tk+!¥)&f_%'Soz`
PTs

Hg(OTf)2(2 mol%)Ac

CH3NO2

H2N N

N
H
25%

178

151b

OTBDPS+($9B6+

¥

OH
+

#¤UnY

¤

Ts

Hg(OTf)2(2 mol%)Ac

CH3NO2

H2N N

186

+

Ac

O
25%

179

N
H
82%

178

Ts
N

Ts
N

185

Ac

O

0%

179

185

Yamamoto, H.; Yamasaki, N.; Yoshidome, S.; Sasaki, I.; Namba, K.; Imagawa, H.; Nishizawa, M. Synlett 2012, 1069

Fig. 21      ¤
)





¤64  AgOTf +]DTk+¥ 64 +mF¤TLC " UV ~e365 nm%¤64 .@8;>Bu(jM

GiaQ)(

(xIFig. 22¥¤Tk

Fb\()¤£^O(N( 64 M+¢'¤Tki¤64 +ZU(¥#¤¤d}¤3/AA4BF¤5 mol% 64  AgOTf +Tk+!Table 14¥sT
ktJ¤Entry 1 %¤*

5 QSo('¤[¡{Vhl¥)¥Tk¤U 52%

R

¤£^OTkw|z`¤183 l+&¤jM+¢',.@8;>7@^Ry 64 +2?.1@.>=/A<60>:,C%c
ZU

¥

47

Hexane:AcOEt = 4:1
UV (365 nm) 

H

HgCl

64



Fig. 22TLC







Entry 1 X@R:CkUES 183 QM8 69 6_


"



L

[

kO 0 °C :C#aEntry 2lJK3k;T

G="k183 # 78%;TB!
D#Wb

d]<\Dl3 mol% 64/AgOTf #V:C

k:CHjAi;T41#F

ZLEntry 3l20Z

kEntry 2 X 0 °Ck5 mol% 64/AgOTf1:1#IeK3l

Table 14 &.*+-).?9Ph#VK3N`
H

OTBDPS
n-C4H9+n-C4H9
182b

Ts

H
N

N
H

HgCl
/AgOTf
(1:1)
64

Boc

CH2Cl2(1.5 eq)

69

Boc

H
N

NTs

n-C4H9n-C4H9183

Entry

64/AgOTf

Temp.

Time

Product(%)a

Recovery (%)
of 64a1

5 mol%

rt

5 min

52

>95

2

5 mol%

0 °C

10 min78>95

3

3 mol%

0 °C

1h

69

>95
a Isolated yield.

 kScheme 26 XkHgOTf2  PhHgCl/AgOTfkg$/'%,kY.$(f#V:C#Wbl
#^5





l
48

k7c 64/AgOTf #0>!K3

Scheme 26 4|I}w!kAT
Catalyst+

182b

・Hg(OTf)2/TMU

183

69

・PhHgCl/AgOTf

CH2Cl2(1.5 eq)・AuCl・Hg(OTf)2

Catalyst(5 mol%)up to 67%

 64/AgOTf !kBi 183 !S







・AuCl3・In(OTf)3a 183 "/%

1HY!}Scheme 27Boc Fv8~G@bs!f{#(/fd!e>

WnxjV 186 Q=qyon7k

3U'.$&/KE2O\<{*'/Fv 187 !t"/%1
jV

188



mz

3U'.$&/!k 186  188 AT9h?`n[c!z;







Scheme 27 183 "/%1<JHYAT

Boc

H
N

N

n-C4H9Ts

HCl in AcOEt

n-C4H9rt, 8 hH
R

quant.

183

H
N

N

Ts

Neutralsilica gel

H

N

R

rt
R
186 R = n-C4H9

H

N
R

R

187

82%

R

188

 a
182b  188 01,)*AT!}Scheme 28. :6n64/AgOTf|I!k 182b  69 "./"-+@AT!xG@bs#(/fd!r3e>RBoc Fv8~

Lu]g3U'.$&/!>ZX^ATN 3 Pp!tlAT

188

jV64 MnDB

Scheme 28 01,)*_5

n-C4H9n-C4H9

182b

+ Ts

H
N



"/%1<JHYAT
HgCl/AgOTf(5 mol%)H

OTBDPS

182b C

Boc

N
H
(1.5 eq)
72

64

HCl

CH2Cl20 °C

49

AcOEt, rt

Neutralsilica gel, rt

HRR
R = n-C4H9
188

Recovery of 64> 95%
64% (3 steps) c_L[`D

%Q@y\rTable 15&$Qa}B);<)96JL[ih(w
5:15 190, 191 (K)<.>S^(~ 0-=8,2>VE 186k#$@W);<7$);<)96JL[({_L[I{ 74%Mk 190 (YEntry 1c190 RJdu

*3<geA\0;+/<(fHBoc QxFxtuJL[({&$L["O{po%0-=8,2>120

zTMkl]

Entry 2 sq);<0;<*?4< 189a$"191a192a S^

Entry 3 s 189b

{%

$ 192b L["'191b

192b xtuJL[CvN(GXbn\J%Z|
MkmL[po 192b (Bl]jY%

$"Uo 64 (PM




$

%!43&

Table 15 Q@y\a} a) 64/AgOTf (1:1)(5 mol%)OTBDPS
R2 +

R1

186, 189

Entry

69(1.5 eq)

CH2Cl2, 0 °C

R1

74%a
> 95%bOTBDPSa) 1 h189a

Ph 84%a Ph> 95%bOTBDPSTsb) HCl in
AcOEtc) Neutral
silica gel

R2

rt

rt

R2

R1

120, 192

190, 191

120, 192b) 18 h c) 36 h

N
Ts

NHBoc
86% (2 steps)

190

BocHN

2

Ph

N

a) 1.5 h

1
186

H
N

190, 191

Substrate

OTBDPS

Boc

120

NTs

b) 8 h c) 5 h

PhPhPh 75% (2 steps)
191a

BocHN
a) 15 min

192a

NTs

b) 72 h c) 32 h

3

189b

81%a
> 95%b43% (2 steps)
191b

192b
a Isolated Yield. b Recovery of 64.

50

 G_^<OFZ-.%-.

1&.K8?NXTable16`DQ)(.;C  189c  191c1  191c2 L@4 57% 18%9IJA]

Entry 1`191c1  191c2 !,+"/*'#,)15]:S_7

 191c1  191c2 _ 

TPR68?3

.$0 191c1, 191c2 =`191c1  E \BM8?[V _72 192c1  75%9IJA`191c2  Z 4H 192c2 E/Z = 15:1>`Table 16 ;Y2U@EW a) 64/AgOTf (1:1)(5 mol%)OTBDPSR +R(1.5 eq)

189

Entry

72

H
N

Boc

N

R

CH2Cl2, 0 °C

Tsb) HCl in
AcOEtc) Neutral
silica gel

R

rt

rt

192

191

Substrate

192

191

BocHN

NTs

OTBDPSb) 3 hc) 24 h75% (2 steps)

Pha) 3 h

Ph

192c1

191c1

57%a

R

R

1

Ph

> 95%b

189c

TsN

NHBoc

b) 6 hc) 24 h72% (2 steps)

Ph(E/Z = 15:1)

Ph

192c2

191c2

18%a

BocHN

NTs
b) 6 hc) 24 h82% (2 steps)H

OTBDPSHa) 3 h191d1

2> 95%b

TsN

192d1

62%a

NHBoc
(E/Z = 4:1)b) 12 h c) 24 h

H

189d

18%a

80% (2 steps)

H
H

191d2

192d2
a Isolated Yield. b Recovery of 64.

51

 pGsfQTr 189d $Y

%@A%<5QSe$n

SeEntry 1 Uo 191d1  191d2 wfI
 191d2 



|QSe

tg

R

! Entry 1 Uo191d1dEntry 2. l
 191d1

 E hx 192d1

tg

191d2

 192d2 E/Z = 4:1

#

#

m

189 $SeY" 69 $u%@A%<5QSeO 44 9D,{ SN2’XSe>'4.=M%@A'0&CvSe"[W""tg
Fig. 23 `"Myers

-A:4AY%A*C E/Z hx

ZV"%@A-A:4A63?,3

Seax 1,5-+);2B7DHSe "47c-e)

j191c2  191d2

JK" 191c1  191d2

γ Hyb"%A(AY}I_c]^ trans-,%/C 193C tg`cis-,%/Ctg

hxtg" E-%A*C tg  #". E

cis-,%/C 193A

I



qP\x

~F"?,'ANt Z#".

A)

H

H
N

R1

N

Ts

-TsH

H

α

R1

γ

β

191c1,d1

B)

Ts

R1

R1

N

γ

α

H
N

β

N

H

1

1,5-sigmatropic
elimination

N

H
β193A (cis-diazene)

Pass A(Major)

H
R2

-TsH

R1

R1

N

γ

α

N

192c1,d1 (E-selective)

1,5-sigmatropic
elimination

H
R2

β

R1
R1

R2

192c2,d2 (E,Z-mixture)

193B (cis-diazene)

191c2,d2

H

R1

γ

α

5

-N2

Pass B(Minor)

-TsH

R1

N

H
N

radical reaction
R1

R1

R2

193C (trans-diazene)

N

H
N

R1

R2
193C1

Fig. 23 %A*C E/Z hf` piY$k"LsfQTr 189e-g ,+B(+81C 189h
52

Se$z

Z

Table 17. 189e 7[` 191esyn/anti = 1:3K=- 192e 3A2;_OW6^"#%+!H4I

_191e H4I_FRNP02;1
Entry 1`.]Q4($*7?

 189f 

189g 2;_U83J1- 191f  191g K=`191f_191g 

RNP02;U8\V

_:;

`

X

2;_0 °C 

_189h 7[, 192h K=

192f  192g K=_S5GL)*'&02;B/"`Table 17 7[-T<CY a) 64/AgOTf (1:1)(5 mol%)OTBDPS
R +

R

189

Entry

72
(1.5 eq)

CH2Cl2, 0 °C

H
N

Boc
R

b) HCl in c) Neutral
silica gel
AcOEt

Ts

N

R

rt

rt

192

191

Substrate

191

OTBDPSa) 6 h

TsN

R

R

192

NHBoc
(syn/anti = 1:3)b) 18 h c) 24 h

1

CH2OEt79%a> 95%b86% (2 steps)

CH2OEt189e

191e

OTBDPSa) 1 hTsN

CH2OEt192e

NHBocb) 14 h c) 24 h

279%a
> 95%b79% (2 steps)

189f

191f

OTBDPS

TsN

192f

NHBoc

a) 4 hb) 48 h c) 12 h

3

OAc

82%a
> 95%b

189g

191g

OTBDPS4OTBDPS

189h

OAc

87% (2 steps)

OAc
192g

a) 4 h
62%a> 95%b192ha Isolated Yield. b Recovery of 64.

189h  192h >92;ED Fig. 24 M
53`@2;_)*'&02

- 194 7

E$0"(A<9>DF

,E!(>DE%+2@*C

7.

Et-!(814;"#6

=



>:;&'-B?

# 195
/5

F

BocHN

N

BocHN

Ts

N

Boc
N
Ts
N
H

Ts
H
OTBDPSOTBDPS

194B

194A

194

Boc
N
N

O

O
H N

N

-TsH
195

196

Fig. 24 184i  189i /)'-32

54

192h

K)L 8?
 AJ

W#$#$'$ 182b

#$!12=W64/AgOTf Q5B,*W0CF
W<

#$"R7- 183 D

X(S2=%&2=3>GH

B,*



=DOTBDPS
n-C4H9n-C4H9

+ Ts

182b

H
N

TO

64

N
H
(1.5 eq)
69

9U


X

Neutralsilica gel, rt

HCl

CH2Cl20 °C

X

TOX+;WUE

HgCl/AgOTf(5 mol%)

Boc

P.

Myers 4NIM12=

0CF

@:

H

/6V

N-Boc-N’-$" 69

H
R

AcOEt, rt

Recovery of 64
> 95%

R

188 R = n-C4H9
64% (3 steps)

H+
BocHN
R

N

Ts

HCl

R
R
= n-C4H9
183

H 2N
R

O O
S
N

Neutralsilica gel

R

ArSO2H

181A

N2

1

H
R

N

H

N
R

5

R

165

m-C2B10H11HgCl/AgOTf-Catalyzed Reaction for Reductive Deoxygenation
Yamasaki, N.; Kanno, M.; Sakamoto, K.; Kasai, Y.; Imagawa, H.; Yamamoto, H.
Synlett 2018, 29, 169-175.

55

R
188

»mº (±)-Oridamycin A YjÖQRj&£ÈU
»L½ ~Ê ¦{oÃ)C92?·¾ªÃ7AHG5<.y&

2?±Û/4E%76Û.DÛ0;3¦uo*ÛL±x)b´Ô°Ó³+]­Ò@-/=K+Ø
*'
)





2?±+³²Ü#Û 2?

ÜÎÛÒ/1IÃbÛqk*).55)

Fig. 25Û«ª

R et D en aquaculture au Canada de 2011

稚魚 （サケ，アユ，ウナギ） 

2?_Æ¤&)Ã¥¡LÂ´)Ü

2?_Û`ÏXS­&Ãb+µ Malachite green 197

T­

*

Fig. 26ÜMalachite green ­Ñ

1 t/h ¢

f.56) Ø*Ús¨©&($ZÅ%i×Ð 100 VOMÒ+Ä¹

魚卵（イクラ）Û'ÛZaz)g(À"¼$Ç*)ÜClustering ﬁsh serial killerrrÑ+

\*

*)

ØÛ#§^±)Fig. 25.54) LÂ´Û×­ÚÙwØ*)¸Ú%eÍ¬­dÆlÉÑx¿ 26 [#vUÛh'>:%c©

³

%Û×vYx)¥ÌÁË'ÛØ®},JWt¯

Ù!

ÛLnT

*

Û2005 |ÆN¡PYÕ¶Ü«oÛ}pÃ8B4:F+) Bronopol198

56



Û

p*7MUA¨P%$$.57) (d`$yb¯g 175 μg/mL h.8>=,5(`$­qm`i

ClN

m'

F

¶Bronopol .8>=,5¶I-14¡Z$. ¶"¶+>=;:0?-~k

XS%$.58)

N

Malachite green (197)

Br

NO2

HO

OH

動物への発がん性/催奇形性の疑い

Fig. 26

 !

Bronopol (198)
日本で唯一の抗水カビ剤

水カビ病に対する動物用医薬品

w¶T³Z\E{".8>=,5(d­qm´p

*7Mr'c®¶2010 e¶t¢14=849)/1d KS84 }"Oridamycin A74'O°¬^.59) 74 ¶.8>=,5(dCV±$6;/2*` 3.0 μg/mL N|'s¶Bronopol ª$ip¢m'Table 18·¶.8>=,5(d`$­qm

´

"¶

Bronopol x&$up*7Ml¶¶Oridamycin }DBPzj%$·

Ym'#«"¶²µ`$_WN|§%·¶*7`$HfK !

w¶£ Oridamycin A ]^JL[3@<H¤o¶Oridamycin A

57

Bv$·

Hf¥vR!©aGQn'¦·

Table 18

Oridamycin A とBronopolとの活性評価

MIC : 最小発育阻止濃度 (μg/mL)

Oridamycin A

Bronopol

Saprolegnia
Parasitica

3.0

175

Chlorella vulgaris(クロレラ)

> 100

0.37

62.5

1.4

NH

HO
HO2C

H

EC50 : 半数遊泳阻害濃度 (μg/mL)

Oridamycin A (74)Daphnia pulex

Streptmyces sp. KS84株
から単離(ミジンコ) \jlvOridamycin A R\jR

b^

%

2015 gN`f Li .IL@>ELFL-5JLK/8HK.

k Trotta "]qr 74 G7BR\j&b^

IL@!$R\j$tu

Scheme 31.60) U.

Snider CuOAc2 &~ 202 " 205 G4+I}YZh 61)
g;,25cf Krische ".IL@ MnOAc3

SV~ %$
|

(H4)

Cd 208 &~'I1LI 206 *A,3= 207 "C-H ziYaMp_
{u

&v

$MpR\j&b^

.62)



%R\j 74 

&8L09<IL<#mw+?WX&oPQ\j+>6CsTe:LI\jyjSPQ\j&[x~iO

 74 R\$x~i\jIL<&n

58

, D



これまでに報告された全合成例

Scheme 311) Li, A.; et al (2015) (Total 9.6% from 199)
2) Trotta, A. H. (2015) (Total 6.6% from 199)
R2

R2

Mn(OAc)3(2 eq)NH

R1

Cu(OAc)2(1 eq)

O

R1 = OH, Br

CO2R3

199

R2 = Indole, OH, OAc
R3 = Me, TMSE
200

X
Mn
(III)

Mn
(II)

CO2R

H
H
(±)-74
X

O

O
RO2C

CO2R

202

HO
HO2C

201

X

Mn(OAc)3O

48-52%O
R3O2C

X

Cu(OAc)2
O
RO2C

H

H

204

203

205

cf . Snider, B. B. Chem. Rev. 1996, 96, 339
Krische, M. J.; et al (2016)

COMe

O(±)-207(R )-IrLn 208
K3PO4
90% yield
34:1 dr 98% ee

HO
206

O

COMe
(+)-74HO
HO

O(Total 14.4%
from 206)

209

Ir

Tol2
P

P
Tol2
CN

NO2

(R )-IrLn 208

 ><91!26 Scheme 32

8G!  B;210 (.*@

4'(.

F64

211 3:G

AgOTf 5FA 4C&C"E;)A?-$)/%0D#

FA 4C,=*9$

'+7



Scheme 32

水銀触媒によるタンデム環化反応を鍵段階とした(±)-オリダマイシン A の全合成研究
OR

H

G

HgCl

OR
NH

64
A

AgOTf
PGO

H
210

PGO

 
59

211

HO
HO2C

H

(±)-74

J (±)-Oridamycin A Q[o
C3-epi M[o# nO

±i¡§¨3A8.GC212$t)

. 63) {±40 mol% Li2CuCl4  THF [}¨`)P)±-EF+EV[

²

Scheme 33±0 °C yKH±TBS ` m-4D04<E4C2B8@ 214 )H
±\u TBDPS `P 72 "

213

±VT¯M 216

.64)

環化前駆体の調製
OR

214: R = TBS (4 eq)
215: R = TBDPS(10 eq)

ClMg

Li2CuCl4(0.4 eq)

OAc
OAc
8 steps (57%)

THF/Et2O (1:2)
15 min, 0 °C

O

212

PMBO

(PMB基)

216: R = TBS>99%
72 : R = TBDPS 98%

213

MeO

 {±64/AgOTf )d

OR

c©VXm)zTable 19² ±51DD?6EI±0 °C yKH±216 )Xm`¢ 20 mol% 64  AgOTf )Xm)!
²Xmk®a}R*G

&±VMN

²xXm$±wj£%±N

 64 )/A>1D=72A;
 64 )fª_Y±VM¨e`.C7±:AnM 1:3 |o$LnM±TBAF #% TBS `)«W
±'')SZ&²k±yKz)©&±px]­Entries 3-5² .C7LM¬g)¦oU

(² ';,9GCbr±.C7F:AnM]­)~±#%h° TBDPS `)v" TBAF R#]­

²

60



±(Y)s^&& 72 )`¢',:ALVXm¥q¤Entry 6²TBDPS `P)¥ql&

&

¤

&

(

±

 73

Table 19

タンデム環化反応の検討

1) H

HgCl

OR

PMBO

HO

OH

64

AgOTf
CH2Cl2, 0 °C

TBAF (1.5 eq)

thenwashed NaCl aq

THF, rt, 1 h+Hquant.
PMBO

216: R = TBS
72 : R = TBDPS

H
PMBO

73

217

Entry

R

64 (mol%)

AgOTf(mol%)

Time

Product (%)a(73 : 217)

Recovery (%)
of 64b

1

216

20

20

10 min76 (3 : 1)

>95

2

216

-

20

1 day

trace (87%)c

-

3

216

20

10

30 min80 (3 : 1)

>95

4

216

10

10

30 min80 (3 : 1)

>95

5

216

5

5

3h

68 (3 : 1)

>95

6

72

10

10

30 min80 (73 only)>95 (>95)da Combined yield of isolated 73 and 217. b Isolated yield. c Recovery of SM.
d Reactions performed on one-pot operation.

 h73 i
0=@[G


T.=3<A.TWb

Buchwald-Hartwig O_!

|Scheme 34.65) dO_XUQ

Yr 219 }[0>TBs TF~

eC.66) z219 !81T

DDQ  PMB TM Dess-Martin

cL4@*@)>5Lx, H\!

>-2/ 221  z A oRvlwguS DBurnell eC

N{,67) 221 J t-BuOK

MeIInnpsr

kP

Kmj!>-2/ 222

;"L:+>^dO_221 VTI MeI O_

(!),?$ar 222 p`]PinnickL 222 !>-2/T#1<A.f:+>TtEZ

%>6@



A oByPl%="9 MeI

q:+>#),> 223 

m-CBPA #7&'/

61

L





Scheme 34

エポキシド体までの合成ルート

OH

OTf Aniline, Cs2CO3
Pd(OAc)2 (10 mol%)
SPhos (15 mol%)

Tf2O
Pyridine
CH2Cl25 min, 0 °C

H
PMBO

73

PhSO2Cl

N

98%

H
PMBO

219

NBs

t-BuOK (5 eq)
Toluene
80 °C, 1 hOS O2) DMP, CH2Cl2
rt, 1 hH98%

2B.

1) NaClO, NaH2PO4
2-methyl-2-butene
THF/t-BuOH/H2O (1:1:2)
rt, 6 h2) MeI, K2CO3
DMF
80 °C, 10 min
2 steps 85%

Fig. 27 &(9

68%

H
221

NBs

m-CPBA

NBs

THF, rt, 24 h
95%
MeO2C

H

223

O
MeO2C

224 BOridamycin A 5>):B;?7%/<07%/!"then
MeI (20 eq)
OHC

220

NBs

222

88% (2 steps)

(Bs基)

PMBO

H

218

1) DDQCH2Cl2/H2O (20:1)
0 °C, 12 h

CH2Cl2/Pyridine (1:1)
18 h, rt

OHC

Toluene12 h, reflux

H
PMBO

quant

NH

3 5>)3
B=:B2 5>)3

*'B:

H

224

$,=

@+#4-A 2 ?

 226 .

Fig. 27C$, 227 B3 ?7!" 228 816.68)

62

NH

CO2Me

3
2

3

O

HO
H
HO2C
Oridamycin A

225

Fig. 27

2

2

RO
MeO2C

H

3

RO

O 3 CO2Me
H

H

226

MeO2C

H

228

227

エポキシドの開環反応における水酸基の位置選択性

 F30Hc]K²224 ¤U¬ TMSBr  TMSOTf "W­Yn"²Lo¢ 2 N­Yn

230

£

²3 N/G*/^"u[p²k²24 s®W¦~6H 229 `rp

²TBAF S²Jq,Scheme 35³230  229 Yn²W¦~ Br ^ ¤U¬ TMSBr x Br–}zrYn&15F/G*/^

£

y

 230 231A ,69) A3F

Vdeg 231B .H<'A&)6E#F¨j

I/CH HBr °

³h¯



³

OY¡²Mk²{"« l! 229 ²Et2O  MeOH [b²>+8/$@v"W

²Jq Bs ^P

,6H¦Q"³m

²  Br ^³

²233 0<%7F#?H§N":D0$@b"ªX;#EIF#4=EH+Yn)F
92IF`r.70) tk²±ªW|TA3F&15F"P

Oridamycin A R[p"¥p
pFI6
1³[p³©ª-D7(IFZ

 74 ²Fig. 28 

H-NMR 3BI6fRJ

"

63

²Mw³

²

10.3%²24 i[
_\

a

Scheme 35(±)-オリダマイシン Aの全合成

NBs

O
MeO2C

H

TMSBr (3 eq)
TMSOTf (3 eq)
2,6-lutidine (6 eq)

then
TBAF

Toluenereflux, 24 h

THF
0 °C, 15 min

NBs

O
MeO2C

One-pot 92%

224

H

TBAF

TMSBr/TMSOTf

2

Br
R

Me

Me

R

Br
inversion BrBr

H(chair )231A

Mg powder

NH

MeOH/Et2O (1:1)
rt, 6 hβ-elimination

TMSO RTMSOH
R = CO2Me
230

Me

H

3

TMSO

TMSO
MeO2C

H

(boat )231B

Pd(OAc)2 (30 mol%)Cu(OAc)2 (2.5 eq)

NH

93%



H

HO
MeO2C

233

H

234

A

1H-NMR (400 MHz in CD OD)3(±)- 
A
1H-NMR (500 MHz in CD3OD)

Fig. 28 

64

H

232

PivOH/Dioxane (1:10)
Air, 115 °C, 56 h

HO
MeO2C

229

1H-NMRNaCN(±)-74DMSO
120 °C, 3 h82%
Total 10.1%(from 212) »Oridamycin A ·RS»±e®SXi& C3-epi-Oridamycin

A239^uwScheme 36¼{^u»Oridamycin A O³S
­¥,E/3; 224$¬l(ª!¼  224 (DM7M¨»TMSBr(WW°¼TLC #% 235 u(«r»:IB9J45=
H+; AIBN (W Br e(µ\ 236 l¼r»Oridamycin A _w¶ Bs e(µ\».J>8NJ¹}(~»z 239 ^u(¯u¼Scheme 36

C3-epi-オリダマイシン Aの合成

NBs

TMSBr (3 eq)

NBs

C6H6 (wet)reflux, 30 min Br
H

HO
MeO2C

224

H

HO
MeO2C

235

Pd(OAc)2 (30 mol%)Cu(OAc)2 (2.5 eq)

Mg
NH

MeOH
rt, 6 h
96%
HO
MeO2C

H

NH

DMSO
120 °C, 3 h

71%

77%

HO
MeO2C

H

238

H

236

NaCN

PivOH/Dioxane (1:10)
Air, 115 °C, 56 h

237

NBs

reflux, 15 min
92% (One-pot
from 224)O
MeO2C

Bu3SnH (6 eq)
AIBN (20 mol%)

NH

3

HO
HO2C

H

C3-epi-Oridamycin A 239

 ^u 74  239 »jogibY¢^vQ£U»2CLK0<*nk&t©Tª¸(¤Table 20¼¡a

ZV

§

»^u Oridamycin A »2CLK0<*?H39.kzm´p

0.5 μg/mL »h Oridamycin A f`#%qt(¼ |d»P]
s$'
&
«





t(&¼[»h#%"ºp 74$ºt

$ ent-Sy&¼"»^ucqx.@t(]t&¼ent-S!t'»x.@tk&A)NF1A-*²¦§
65

H6GS

&

:Tzyrt@HZZ

37,!Ip?JACB!n ent-<A9]^q}U zy[f$/B

`S



Vn!}\74  239 1)6'OWXgM!{vhGDocbOECD+*,%#-2#6jiK

wa,71) (054&."Ea!s_EkQ 50 =100 =;8kQ1)6'eX~NRP[f$/B>|FHl q}mYu

LdVn`Sx



Table 20

サプロレグニア属に対する生物活性評価とミジンコ急性遊泳阻害試験

富山大学

和漢医薬学総合研究所

伊藤卓也

先生との共同研究

Br

NO2

HO

OH

NH

NH

HO
HO2C

H

HO
HO2C

H

最小発育阻止濃度 (μg/mL)

ブロノポール

Saprolegnia Parasitica

175a

天然物
合成品

3.0b
0.5

1.0

Saprolegnia Subterranea

-

天然物
合成品

0.5

1.0

92

50

(±)-74239

EC50 : 半数遊泳阻害濃度 (μg/mL)
Daphnia pulex(ミジンコ)

1.4aa Flores S. et. al., Int. J. Mol. Sci. 2016, 17, 1366

b Takada, K. et. al., J. Nat. Prod. 2010, 73, 698

66         f4g IQ
 Se~PY*ZNb64  AgOTf \S}TUh72  73 $2&-[?AM=\~Oridamycin A ;COqO'~73 t5v9
C3-epi 9 239 COH

tXx

ad

SCO/3

V{79CORKGy Oridamycin A PjZNn:~Oridamycin A ~4[ND~Oridamycin A <~",10!().#%

PjZNJz@RK

Oridamycin A ;CO`ck~"+'0(

UpZN^w~3 8YrDd9?E
slFiDao

{79G|W=\BiPY

6L~_m
*>u]





NH

1) H

Total 18.1%(from 72)

HgCl
64
(10 mol%)

TBDPSOAgOTf (10 mol%)
CH2Cl2, 0 °C, 30 min

HO
HO2C

H

(±)-Oridamycin A (74)
MIC = 0.5 μg/mL(Saprolegnia Parasitica)

OH

2) TBAF (1.5 eq)
THF, rt, 1 h
H
PMBO

72

PMBO
80% (2 steps)
Recovery of 64 >95%

73

NH

Total 16.6%(from 72)

HO
HO2C

H

C3-epi-Oridamycin A 239
MIC = 1.0 μg/mL(Saprolegnia Parasitica)67s |¥v “+)'*#+!-(

²«£^z

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YR<HK

+"&
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t

³

 %$²w¡«QmL#9/37.9\O«

M

²|L AgOTf

!89[¨r 1,3-Gi(";OQm® %$²#9/37.9«\n«ªd37.9«\,827=,

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 %$²#9/37.9\O« AgOTf£^!89'89"=*9

 N-Boc-N’-,'90-7(-J_¯VhoQm®³ ²l!890-7(-OV Myers [©EOQm®oN³²#9/37.9\O«YRUQmL %$²#9/37.9\O« AgOTf²q#1n²VoOridamycin A  C3-epi-Oridamycin A FVonBOV



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¢WwTec@{j

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P¿\vhhµXjtL¨£h¾£D£²
hP¿hZdH¾BE'?E19AE'En¦¿V¤

B:,!>3E(TLC) Merck Kiselgel 60F 254(0.25 mm)P¿%9),

U 250 nm [ 356 nm  UV >C5m¾2½ p-/%@+2--5% ²'0E@u¾W"@

U¿¾=

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n$?"@ 60 (¾63-210 mm)¾¯n$?"@>;E.>*%B:,!>3¨ Cosmosil 140 C18-PREP  75 C18-OPN P¿

B:,!>3EPh v:v(HPLC)}~VR¨ JASCO PU-987 e,9C5

$?

¾Ua¿»°N

B:,!>3E

B:,9C5¾JASCO PU-2080plus e

B:}~VR¨ JASCO UV-970 eUa¾JASCO

UV-2075 eUa¾o¨Ox¨ RID-10A eUa¿w+E'



|Rs([α]D)¾}~VRJASCO P-1030e|R©k¿®f¢`]%7,@(KHIR

¾\m

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)}~VRJASCO FT-IR410ek¿,@(NMR )¾Varian¨ Gemini-200e, Unity-200e, Mercury-300

e, MR-400e, Mercury-500e, Unity-600e¾Bruker¨ U5BE4BBO
cryoprobeAVANCE III HD 500 MHz spectrometer C(TMS)T±k¿¾kh³¾*,><(@$>

BB8@;(CDCl3)¾³6

C&C(C6D6)¾³DMSO(C2D6SO2)¾³<'0E@(CD3OD)¿Xj$3,(d)ppm
YM§ª¾¡_kz(J)HzYM

k¿$!.@¾F³¢s, I³¢d, G³¢t, b³¢q, J³¢quin.¾g³¢m´V%7,@(KHMS¿qrQ^br)¾}~¸i¨ AX-500e
69

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/(CI3);#
C2Si HDMS
;68

:7"'

!/(FAB3)Waters45 SYNAPT

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70

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WV

(E)-N-(Hepta-4,6-dienyl)-4-methylbenzenesulfonamide (61)

NHTs
61

(E)-Hepta-4,6-dien-1-ol19) (1.0 g, 8.9 mmol)

CH2Cl2 (30 mL)FA

DMAP (220 mg, 1.8 mmol), MsCl (1.2 g, 10.7 mmol)  0 °C
30 +[;:`07B1LZ
mL)8GA
E_NEt3 (4.5 g, 44.5 mmol),-5_UN@C- CH2Cl2

9*_=>OJ@P'K_IX5HT`6?D TsNH2
120 °C-5_

E4)/5_UN@C- Et2O

KOH

DMF (20

2 <[;:`07B1L3

9*`=>OJ@PZ'K_IX5HT`6?D!
YZ" 10:1)

E4

#!%($/SV 61 (1.7 g, 73%)6`61: colorless syrup, FT IR (neat) 3283,

3085, 3063, 3025, 3014, 2929, 2868, 1651, 1599 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.56
(2H, quin, J = 7.2 Hz), 2.07 (2H, dt, J = 7.2, 6.9 Hz), 2.43 (3H, s), 2.94 (2H, dt, J = 6.0, 7.2 Hz),4.70 (NH, br t, J = 6.0 Hz), 4.97 (1H, br d, J = 10.2 Hz), 5.07 (1H, br d, J = 17.1 Hz), 5.56 (1H,
dt, J = 6.9, 15.3 Hz), 5.98 (1H, br dd, J = 10.2, 15.3 Hz), 6.25 (1H, ddd, J = 10.2, 10.2, 17.1 Hz),7.30 (2H, br d, J = 8.1 Hz), 7.75 (2H, br d, J = 8.1 Hz); 13C NMR (75 MHz in CDCl3) δ 21.54,
29.00, 29.40, 42.60, 115.50, 127.07, 129.69, 131.94, 133.19, 136.82, 136.88, 143.37; HRMS(CI+) m/z calcd for C14H20O2NS [M++H] 266.1215, found 266.1205.

(E)-N-(2,2-Dimethylhepta-4,6-dien-1-yl)-4-methylbenzenesulfonamide (108a)

NHTs
108a

(E)-2,2-Dimethylhepta-4,6-dien-1-amine27) (140 mg_1.0 mmol)
71

CH2Cl2 (5 mL)FA , Et3N

(0.43 mL, 3.0 mmol) DMAP (24.4 mg, 0.2 mmol)3G
L

TsCl (229 mg, 1.2 mmol) 0 °C

E,

E,

.7*AY=?L Et2O

Y3G

,. @Y.7D/

1 <T;:. W1V2C

9+Z=?MJCNS!")KYIR4HPZ6BF$%#"&!#((

'/AcOEt 5:1) OQ

108a (244 mg, 83X)6Z108a: white powder; FT IR(neat) 3285, 3085, 3035, 3008, 2963, 2926, 2871, 1650 cm-1; 1H NMR (300 MHz in CDCl3) δ
0.86 (6H, s), 1.98 (2H, d, J = 7.5 Hz), 2.43 (3H, s), 2.68 (2H, d, J = 7.2 Hz), 4.35 (NH, t, J = 7.2
Hz), 5.00 (1H, br d, J = 10.2 Hz), 5.10 (1H, br d, J = 16.5 Hz), 5.58 (1H, dt, J = 7.5, 14.7 Hz),6.00 (1H, dd, J = 10.2, 14.7 Hz), 6.26 (1H, dt, J = 10.2, 16.5 Hz), 7.30 (2H, d, J = 7.8 Hz), 7.72
(2H, d, J = 7.8 Hz); 13C NMR (75 MHz in CDCl3) δ 21.45, 24.83, 34.58, 42.44, 52.74, 115.42,
126.97, 129.61, 130.25, 133.93, 136.83, 143.16; HRMS (CI+) m/z calcd for C16H24NO2S[M+H]+ 294.1528, found 294.1522.

4-Methyl-N-(2-(penta-2,4-dien-1-yl)phenyl)benzenesulfonamide (108b)(E:Z = 4:1)

NHTs
108b

-/L 108a0>8U

5

Y(E)-2-(Penta-2,4-dien-1-yl)aniline72) (382 mg, 2.4 mmol)

 108b (722 mg, 96%)6Z108b: white powder; FT IR (neat) 3278, 3083, 3065, 3034,
3011, 2971, 2924, 1650, 1599 cm-1; (E-isomer) 1H NMR (300 MHz in CDCl3) δ 2.39 (3H, s),3.10 (2H, d, J = 6.3 Hz), 5.04 (1H, br d, J = 10.2 Hz), 5.10 (1H, br d, J = 17.1 Hz), 5.59 (1H, dt,
J = 6.3, 15.3 Hz), 5.90 (1H, dd, J = 10.2, 15.3 Hz), 6.25 (1H, dt, J = 10.2, 17.1 Hz), 6.57 (NH,br s), 7.08 (3H, m), 7.21 (2H, d, J = 8.4 Hz), 7.37 (1H, d, J = 7.8 Hz), 7.60 (2H, d, J = 8.4 Hz);
(E-isomer) 13C NMR (75 MHz in CDCl3) δ 21.56, 34.55, 116.95, 124.39, 126.25, 127.13,
127.61, 129.56, 130.41, 131.04, 132.47, 132.71, 134.64, 136.14, 136.57, 143.79; HRMS (CI+)
m/z calcd for C18H19NO2S [M]+ 313.1136, found 313.1136.

(E)-4-Methyl-N-(octa-5,7-dien-2-yl)benzenesulfonamide (108c)
72

NHTs
108c

 108a (E)-Octa-5,7-dien-2-amine73) (37.5 mg, 0.3 mmol)

108c (80.7 mg, 96%) 108c: white powder; FT IR (neat) 3278, 3083, 3065, 3034, 3011,
2971, 2924, 1650, 1599 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.03 (3H, d, J = 6.3 Hz), 1.46
(2H, q, J = 8.1 Hz), 2.03 (2H, m), 2.43 (3H, s), 3.32 (1H, m), 4.21 (NH, br d, J = 8.4 Hz), 4.98
(1H, br d, J = 10.2 Hz), 5.07 (1H, br d, J = 16.8 Hz), 5.53 (1H, dt, J = 6.9, 15.3 Hz), 5.93 (1H,
dd, J = 10.2, 15.3 Hz), 6.25 (1H, dt, J = 10.2, 16.8 Hz), 7.30 (2H, d, J = 8.7 Hz), 7.76 (2H, d, J
= 8.7 Hz); 13C NMR (75 MHz in CDCl3) δ 21.49, 21.56, 28.44, 36.76, 49.44, 115.17, 127.01,
129.62, 131.48, 133.70, 136.97, 138.10, 143.17; HRMS (CI) m/z calcd for C15H22NO2S [M+H]+
280.1371, found 280.1386.

(E)-4-Methyl-N-(1-phenylhepta-4,6-dien-1-yl)benzenesulfonamide (108d)

Ph

NHTs
108d

 108a mmol) 108d (94.4 mg, 92%)

(E)-1-Phenylhepta-4,6-dien-1-amine21) (56.4 mg, 0.3
108b: colorless syrup; FT IR (neat) 3277, 3085, 3063,

3031, 3007, 2971, 2925, 2859, 1805, 1651, 1600 cm-1; 1H NMR (300 MHz in CDCl3) δ
1.77-2.05 (4H, m), 2.36 (3H, s), 4.27 (1H, q, J = 7.2 Hz), 4.74 (NH, m), 4.98 (1H, br d, J = 10.2
Hz), 5.08 (1H, br d, J = 17.1 Hz), 5.57 (1H, dt, J = 6.6, 15.0 Hz), 5.94 (1H, dd, J = 10.2, 15.0Hz), 6.26 (1H, dt, J = 10.2, 17.1 Hz), 6.98 (2H, m), 7.12 (2H, d, J = 8.4 Hz), 7.16 (3H, m), 7.53
(2H, d, J = 8.4 Hz); 13C NMR (75 MHz in CDCl3) δ 21.42, 28.74, 36.87, 57.78, 115.33, 126.49,
127.01, 127.30, 128.39, 129.25, 131.83, 133.22, 136.94, 137.54, 140.59, 142.90; HRMS (CI)m/z calcd for C20H24NO2S [M+H]+ 342.1528, found 342.1520.

(E)-4-Methyl-N-(octa-5,7-dienyl)benzenesulfonamide (114a)

73

NH
O
S
O

114a

 61 



114a (305 mg, 78%)(E)-Octa-5,7-dien-1-amine19) (189 mg, 1.5 mmol)

114a: colorless syrup; FT IR (neat) 3285, 3084, 3063, 3029, 3006,

2930, 2861, 1651, 1599 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.32-1.52 (4H, m), 2.03 (2H, dt,
J = 6.9, 7.5 Hz), 2.43 (3H, s), 2.94 (2H, dt, J = 6.3, 6.6 Hz), 4.28 (NH, br t, J = 6.3 Hz), 4.97
(1H, br d, J = 10.2 Hz), 5.08 (1H, br d, J = 17.1 Hz), 5.60 (1H, dt, J = 6.9, 15.3 Hz), 5.99 (1H,
dd, J = 10.5, 15.3 Hz), 6.27 (1H, dt, J = 10.2, 17.1 Hz), 7.30 (2H, d, J = 8.4 Hz), 7.73 (2H, d, J
= 8.4 Hz); 13C NMR (75 MHz in CDCl3) δ 21.52, 25.98, 28.98, 31.82, 43.00, 115.07, 127.06,
129.66, 131.40, 134.29, 136.90, 137.02, 143.31; HRMS (CI) m/z calcd for C15H22NO2S [M+H]+
280.1371, found 280.1363.

(E)-2,4,6-Trimethyl-N-(octa-5,7-dien-1-yl)benzenesulfonamide (114b)

NH
O
S
O

114b

 108a (E)-Octa-5,7-dien-1-amine (100 mg, 0.8 mmol)

2,4,6-trimethylbenzenesulfonyl chloride (MtsCl) (210 mg, 1.0 mmol) 114b (227 mg, 92%)
114b: white powder; FT IR (neat) 3304, 3087, 3033, 2972, 2937, 2859, 1651, 1604,
1565 cm-1; 1H NMR (300 MHz in CDCl3) d 1.36 (2H, m), 1.46 (2H, m), 2.01 (2H, q, J = 6.6
Hz), 2.30 (3H, s), 2.64 (6H, s), 2.89 (2H, q, J = 6.9 Hz), 4.50 (NH, br t, J = 6.3 Hz), 4.96 (1H,
br d, J = 9.9 Hz), 5.08 (1H, br d, J = 16.8 Hz), 5.58 (1H, dt, J = 6.9, 15.0 Hz), 5.98 (1H, dd, J =9.9, 15.0 Hz), 6.27 (1H, dt, J = 9.9, 16.8 Hz), 6.96 (2H, s); 13C NMR (75 MHz in CDCl3) δ
21.70, 23.74, 26.82, 29.76, 32.58, 43.16, 115.91, 132.23, 132.72, 135.01, 137.80, 139.81,
74

142.90; HRMS (CI) m/z calcd for C17H26NO2S [M+H]+ 308.1684, found 308.1681.

(E)-N-(2,2-Dimethylocta-5,7-dien-1-yl)-2,4,6-trimethylbenzenesulfonamide (114c)

NH
Mts
114c

 108a (E)-2,2-Dimethylocta-5,7-dien-1-amine 73) (100 mg, 0.7mmol)  MtsCl (175 mg, 0.8 mmol) 114c (226 mg, 96%) 114c: white powder;
FT IR (neat) 3308, 3032, 2962, 2935, 2871, 1651, 1604, 1566 cm-1; 1H NMR (300 MHz in
CDCl3) δ 0.83 (6H, s), 1.23 (2H, m), 1.89 (2H, m), 2.30 (3H, s), 2.62 (2H, d, J = 6.9 Hz), 2.64
(6H, s), 4.43 (NH, br t, J = 6.9 Hz), 4.96 (1H, br d, J = 10.2 Hz), 5.08 (1H, br d, J = 17.1 Hz),5.57 (1H, dt, J = 6.9, 15.3 Hz), 5.97 (1H, dd, J = 10.2, 15.3 Hz), 6.26 (1H, dt, J = 10.2, 17.1 Hz),6.96 (2H, s); 13C NMR (75 MHz in CDCl3) δ 20.93, 22.96, 24.92, 26.84, 33.65, 38.67, 52.13,
114.92, 130.83, 131.93, 133.40, 134.90, 137.08, 138.95, 142.10; HRMS (CI) m/z calcd for
C19H30NO2S [M+H]+ 336.1997, found 336.1988.

N-[2-(Hexa-3,5-dien-1-yl)phenyl]-2,4,6-trimethylbenzenesulfonamide (114d)(E:Z = 10:1)

NH
Mts
114d

 108a (E)-2-(Hexa-3,5-dien-1-yl)aniline27) (114 mg, 0.8 mmol)

 MtsCl (220 mg, 1.0 mmol) 114d (271 mg, 95%)

114d: colorless syrup; FT IR(neat) 3286, 3081, 3033, 3005, 2974, 2937, 2871, 2852, 1651, 1603 cm-1; (E-isomer) 1H NMR(500 MHz in CDCl3) δ 2.29 (2H, q, J = 7.0 Hz), 2.31 (3H, s), 2.51 (6H, s), 2.62 (2H, t, J = 7.0Hz), 5.02 (1H, br d, J = 10.0 Hz), 5.13 (1H, br d, J = 17.0 Hz), 5.68 (1H, dt, J = 7.0, 15.0 Hz),6.05 (1H, dd, J = 10.5, 15.0 Hz), 6.30 (1H, dt, J = 10.0, 17.0 Hz), 6.32 (NH, br s), 6.90 (1H, d, J
= 8.0 Hz), 6.94 (2H, s), 7.06 (1H, t, J = 8.0 Hz), 7.13 (1H, t, J = 8.0 Hz), 7.16 (1H, d, J = 8.0
Hz); (E-isomer) 13C NMR (125 MHz in CDCl3) δ 20.99, 23.15, 30.56, 32.94, 115.78, 125.38,
75

126.72, 126.88, 129.89, 132.03, 132.06, 133.32, 133.91, 134.27, 136.50, 136.84, 139.24,
142.53; HRMS (CI) m/z calcd for C21H26NO2S [M+H]+ 356.1702, found 356.1704.

(E)-1-(Hepta-4,6-dienyl)-3,5-dimethoxybenzene (117a)

OMe
MeO



117a

 19 

117a: colorless syrup; FT IR (neat) 3083,

3036, 2998, 2935, 2852, 2837, 1595 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.71 (2H, m), 2.12
(2H, dt, J = 6.9, 7.2 Hz), 2.55 (2H, t, J = 7.8 Hz), 3.76 (6H, s), 4.95 (1H, br d, J = 10.2 Hz),5.08 (1H, br d, J = 16.8 Hz), 5.70 (1H, dt, J = 6.9, 15.0 Hz), 6.06 (1H, dd, J = 10.5, 15.0 Hz),6.29 (1H, t, J = 2.1 Hz), 6.31 (1H, dt, J = 10.2, 16.8 Hz), 6.33 (2H, br d, J = 2.1 Hz); 13C NMR(75 MHz in CDCl3) δ 30.58, 32.01, 35.64, 55.17, 97.64, 106.43, 114.85, 131.33, 134.77, 137.19,
144.69, 160.66; HRMS (CI) m/z calcd for C15H21O2 [M+H]+ 233.1541, found 233.1543.

(E)-Dimethyl 2-(3,5-dimethoxybenzyl)-2-(penta-2,4-dien-1-yl)malonate (117b)
MeO2C

CO2Me

OMe
MeO



117b

 19 

117b: white powder; FT IR (neat) 3085, 3001,

2952, 2839, 1747, 1611 cm-1; 1H NMR (300 MHz in CDCl3) δ 2.61 (2H, d, J = 7.5 Hz), 3.18
(2H, s), 3.73 (6H, s), 3.75 (6H, s), 5.04 (1H, br d, J = 9.9 Hz), 5.14 (1H, br d, J = 16.2 Hz), 5.59
(1H, dt, J = 7.5, 15.0 Hz), 6.12 (1H, dd, J = 9.9, 15.0 Hz), 6.23 (2H, d, J = 2.4 Hz), 6.29 (1H, dt,
J = 9.9, 16.2 Hz), 6.23 (1H, br t, J = 2.4 Hz); 13C NMR (75 MHz in CDCl3) δ 35.40, 38.53,
52.40, 55.14, 59.09, 98.87, 107.99, 116.55, 128.04, 135.16, 136.56, 137.89, 160.54, 171.09;
HRMS (CI) m/z calcd for C19H24O6 [M+H]+ 348.1574, found 348.1573.

76

(E)-N-(3,5-Dimethoxybenzyl)-4-methyl-N-(penta-2,4-dien-1-yl)benzenesulfonamide (117c)
TsN

OMe
MeO
117c

2W?R 19

5B;`

8YXc117c: white powder; FT IR (neat) 3087, 3036,

3000, 2970, 2871, 2839, 2255, 1614 cm-1; 1H NMR (300 MHz in CDCl3) δ 2.44 (3H, s), 3.73
(6H, s), 3.79 (2H, d, J = 6.6 Hz), 4.26 (2H, s), 5.05 (1H, br d, J = 9.6 Hz), 5.11 (1H, br d, J =16.5 Hz), 5.34 (1H, dt, J = 6.9, 15.3 Hz), 5.94 (1H, dd, J = 9.6, 15.3 Hz), 6.16 (1H, dt, J = 9.6,
16.5 Hz), 6.36 (2H, s), 7.31 (2H, d, J = 8.4 Hz), 7.74 (2H, d, J = 8.4 Hz); 13C NMR (75 MHz in
CDCl3) δ 21.51, 48.44, 50.39, 55.30, 99.92, 106.09, 117.98, 127.22, 129.69, 135.14, 135.74,
137.49, 138.29, 143.28, 160.86; HRMS (CI) m/z calcd for C21H26NO4S [M+H]+ 388.1583,
found 388.1582.

%!$%G^6

YX+]1, 97
H
Hg

97

H

m-%!$'(360 mgb
2.5 mmol)

THF (10 mL)LH

bt-BuLi (1.75 mL)-78℃J0bI4Q 0 °C  30 /_>=cD
2.5 mmol)

THF (15 mL)LH 0 °C I4Q

''LH) 1.59 Mb
b61G^(830 mgb

0b0 °C  1 @_>=c1 M HCl

J03:-EbAcOEt <.bGS AcOEt <.cACSO
GT\"#*PbNZ7MVc9

FK$#&"$(('/[\% 5:1)UX 97 (723 mgb60a)9c97: white powder;1

H NMR (300 MHz in CD3OD) δ 1.30-3.30 (20H, m, B10H10 x 2), 3.44 (2H, br s, CH x 2); 13C

NMR (125 MHz in CD3OD) δ 60.09, 60.53, 74.78, 83.92; HRMS (CI+) m/z calcd for
C4H22B20Hg [M]+ 492.3289, found 492.3280.
77o-Carbaboranyl(phenyl)mercury (102)

Hg
H

102

o-($'*(360 mg`2.5 mmol)
1.75 mL)-78℃

THF (10 mL)LG

I4`H7R 0 °C

'(785 mg`2.5 mmol)`t-BuLi (#**LG. 1.59 M`

30 3]?>aC
H7R

THF (15 mL)LG 0 °C

>a1 M HCl I46<0D`AcOEt
aABSPFT[%&`!(F\)4`0 °C=2`FS AcOEt/Q`OY:NVa;'&)%'!+("*/Z[( 10:1)

1 @]?
=2

EJ

UW 102 (208 mg`30_);a102: white powder; 1H NMR (400 MHz in CDCl3) δ 1.30-3.20 (10H, m, B10H10), 3.62 (1H,
br s, CH), 7.27 (2H, m, CH x 2), 7.42 (3H, m, CH x 3); HRMS (CI+) m/z calcd for C8H16B10Hg[M]+ 424.1889, found 424.1869.

o-Carbaboranylmercuric chloride (95)
HgCl

H
95

o-($'*(360 mg`2.5 mmol)
1.75 mL)-78℃

THF (10 mL)LG

I4`H7R 0 °C

'(785 mg`2.5 mmol)`t-BuLi (#**LG. 1.59 M`

30 3]?>aC

THF (15 mL)LG 0 °C

>a1 M HCl I46<0D`AcOEt
aABSPFT[%&

CH2Cl2 (25 mL) LX`0 °C

15aC-`

K9

ABSPFT[%4`0 °C:`^8FI4 Et2O

=2

EJ

`ICl (773 mg, 4.8 mmol) 0 °C

/Q`OY:NVa;)%'!+("*/Z[( 5:1)

1 @]?

=2`FS AcOEt/Q`OY:NVa;,@]?>a&H7R`!(F\)

M

=2a

EJ'&

UW 95 (341 mg, 41%);a95:

white solid; m.p. 289 °C; 1H NMR (300 MHz in CD3OD) δ 1.30-3.30 (10H, m, B10H10), 3.40
78

(1H, br s, CH); 13C NMR (125 MHz in CD3OD) δ 62.36, 78.98; HRMS (CI+) m/z calcd forC2H11ClB10Hg [M]+ 382.1186, found 382.1207. 95 (100 mg) was crystallized from AcOEt (3mL) at room temperature. CCDC 862694 contains the supplementary crystallographic data.
This data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.

m-Carbaboranyl(phenyl)mercury (103)

Hg

H

103

 102 m-

(360 mg2.5 mmol) 103 (488 mg,

46%) 103: white powder; 1H NMR (400 MHz in CDCl3) δ 1.50-3.01 (10H, m, B10H10),
3.06 (1H, br s, CH), 7.25 (2H, m, CH x 2), 7.43 (3H, m, CH x 3); HRMS (CI+) m/z calcd for
C8H16B10Hg [M]+ 424.1889, found 424.1905.

m-Carbaboranylmercuric chloride (64)
H

HgCl

64

79

/1I 95

2=

:T

6

Um-(#&*(360 mgU2.5 mmol) 64 (540 mg, 56%)

7V64: white solid; m.p. 280 °C; 1H NMR (300 MHz in CD3OD) δ 1.30-3.30 (10H, m,
B10H10), 3.49 (1H, br s, CH); 13C NMR (125 MHz in CD3OD) δ 60.36, 75.08; HRMS (CI+) m/z
calcd for C2H11ClB10Hg [M]+ 382.1186, found 382.1196. 64 (100 mg) was crystallized from
AcOEt (4 mL) at room temperature. CCDC 862695 contains the supplementary
crystallographic data. This data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

J/,

19

2-Allyl-1-tosylpyrrolidine (63)N
Ts
63UAgOTf (51.4 mg, 0.2 mmol)3E

64 (76 mg, 0.2 mmol)

CH2Cl2 (20 mL)FB

5U

20 -S<;V>



E4mL)FB 0 °C

C1I(

UQR(

P

.U0 °C

U61 (1.32 g, 5.0 mmol).

H@ CH2Cl2 (3070 -S<;V08C1ITK'

AO5UGMV7?D&%)$&!+("*/QR( 10:1)

LN

63 (1.31 g, 99.2%)7V63:

white powder, FT IR (neat) 3075, 2975, 2875, 1640, 1598 cm-1; 1H NMR (300 MHz in CDCl3)80δ 1.44-1.83 (4H, m), 2.28 (1H, m), 2.43 (3H, s), 2.59 (1H, m), 3.16 (1H, dt, J = 7.2, 10.2 Hz),3.39 (1H, m), 3.66 (1H, m), 5.07 (1H, br d, J = 7.8 Hz), 5.09 (1H, br d, J = 15.9 Hz), 5.79 (1H,
ddt, J = 6.9, 7.8, 15.9 Hz), 7.31 (2H, d, J = 8.4 Hz), 7.73 (2H, d, J = 8.4 Hz); 13C NMR (75MHz in CDCl3) δ 21.55, 23.98, 30.07, 40.88, 49.20, 59.69, 117.62, 127.50, 129.62, 134.61,
134.76, 143.26; HRMS (CI+) m/z calcd for C14H20NO2S [M+H]+ 266.1215, found 266.1203.
Purity of 63 (62:63 ratio) was determined by HPLC analysis in comparison with the 49:51
mixture of 62 and 63 as an authentic sample (which was afforded from Table 1, Entry 1).
[normal phase column (MOMURA CHEMICAL, DEVELOSIL 60-5, Mfg. No. 1502425, 250 x
10 mmI.D.), hexane/AcOEt, 10:1, 2.0 mL/min, detection at 245 nm, tR 33.0 min (62) and 36.0
min (63)].

63
62:63 rate (49:51)

62:63 rate (-:>99)
62 63

2-Allyl-4,4-dimethyl-1-tosylpyrrolidine (109a)

N
Ts
109a

 63 



108a (28 mg, 0.1 mmol) 109a (26.5 mg, 95%)

109a: colorless syrup; FT IR (neat) 3073, 2959, 2927, 2873, 1639, 1599 cm-1; 1H NMR (300
MHz in CDCl3) δ 0.51 (3H, s), 1.02 (3H, s), 1.51 (1H, dd, J = 9.0, 12.9 Hz), 1.64 (1H, dd, J =7.2, 12.9 Hz), 2.40 (1H, m), 2.43 (3H, s), 2.80 (1H, m), 3.12 (2H, s), 3.65 (1H, ddt, J = 3.3, 7.2,
9.0 Hz), 5.07 (1H, br d, J = 9.9 Hz), 5.09 (1H, br d, J = 17.1 Hz), 5.14 (1H, ddt, J = 7.2, 9.9,
17.1 Hz), 7.31 (2H, d, J = 7.8 Hz), 7.73 (2H, d, J = 7.8 Hz); 13C NMR (75 MHz in CDCl3) δ81

21.55, 25.85, 26.36, 37.26, 40.57, 45.52, 59.48, 61.54, 117.73, 127.43, 129.54, 134.33, 135.37,
143.22; HRMS (CI) m/z calcd for C16H24NO2S [M+H]+ 294.1528, found 294.1512.

2-Allyl-1-tosylindoline (109b)

N
Ts
109b

 63 



108b (31.3 mg, 0.1 mmol) 109b (29.4 mg, 94%)109b: colorless syrup; FT IR (neat) 3074, 3046, 3031, 2977, 2953, 2923, 2854, 1641, 1599
cm-1; 1H NMR (300 MHz in CDCl3) δ 2.34 (3H, s), 2.38 (1H, m), 2.60 (2H, m), 2.72 (1H, dd, J= 9,3, 16.2 Hz), 4.29 (1H, m), 5.08 (1H, br d, J = 10.2 Hz), 5.09 (1H, br d, J = 17.4 Hz), 5.79
(1H, ddt, J = 7.2, 10.2, 17.4 Hz), 7.02 (2H, br d, J = 6.3 Hz), 7.15 (2H, d, J = 8.1 Hz), 7.20 (1H,m), 7.52 (2H, d, J = 8.1 Hz), 7.65 (1H, d, J = 8.1 Hz); 13C NMR (125 MHz in CDCl3) δ 21.52,
33.07, 41.00, 61.63, 117.41, 118.34, 124.69, 125.11, 126.98, 127.67, 129.54, 132.02, 133.36,
135.17, 141.41, 143.77; HRMS (CI) m/z calcd for C18H20NO2S [M+H]+ 314.1215, found314.1211.

2,5-trans-2-Allyl-5-methyl-1-tosylpyrrolidine (109c)

N
Ts
109c

 63 



108c (30.0 mg, 0.1 mmol) 109c (29.4 mg, 98%)109c: colorless syrup; FT IR (neat) 3075, 2969, 2930, 2872, 1638, 1599 cm-1; 1H NMR (600MHz in CDCl3) δ 1.32 (3H, d, J = 6.3 Hz), 1.46 (2H, m), 1.57 (1H, m), 1.63 (1H, m), 2.31 (1H,
ddd, J = 1.1, 6.7, 13.9 Hz), 2.43 (3H, s), 2.62 (1H, ddd, J = 1.2, 5.6, 13.9 Hz), 3.67 (1H, m),
3.68 (1H, m), 5.07 (1H, dd, J = 2.4, 10.8 Hz), 5.09 (1H, dd, J = 2.4, 17.4 Hz), 5.80 (1H, ddt, J =7.2, 10.8, 17.4 Hz), 7.30 (2H, d, J = 8.4 Hz), 7.73 (2H, d, J = 8.4 Hz); 13C NMR (150 MHz in
CDCl3) δ 21.48, 23.23, 28.80, 31.93, 41.39, 57.49, 61.21, 117.45, 127.53, 129.56, 134.75,
82

135.20, 143.14; HRMS (CI) m/z calcd for C15H22NO2S [M+H]+ 280.1371, found 280.1386.

2,5-trans-2-Allyl-5-phenyl-1-tosylpyrrolidine (109d)

N
Ts

Ph

109d

 63 



108d (54.0 mg, 0.16 mmol) 109d (48.9 mg, 92%)

109d: colorless syrup; FT IR (neat) 3064, 3029, 2975, 2942, 2872, 1871, 1811, 1734,
1640, 1599 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.61 (2H, q, J = 6.9 Hz), 1.90 (2H, m), 2.38
(1H, m), 2.43 (3H, s), 2.85 (1H, m), 3.86 (1H, m), 4.69 (1H, t, J = 6.9 Hz), 5.09 (1H, br d, J =9.3 Hz), 5.11 (1H, br d, J = 17.1 Hz), 5.82 (1H, ddt, J = 7.5, 9.3, 17.1 Hz), 7.29 (5H, m), 7.37
(2H, t, J = 7.2 Hz), 7.70 (2H, d, J = 8.1 Hz); 13C NMR (75 MHz in CDCl3) δ 21.49, 29.14,
34.23, 41.19, 61.57, 64.79, 117.57, 126.19, 126.98, 127.63, 128.26, 129.58, 134.72, 134.87,
142.57, 143.38; HRMS (CI) m/z calcd for C20H24NO2S [M+H]+ 342.1528, found 342.1523.

2-Allyl-1-tosylpiperidine (115a), (E)-2-(Prop-1-enyl)-1-tosylpiperidine (116a)

N
S

O
O

115a

 63 

N
S

O
O

116a



(33.2 mg, 98%)

114a (33.8 mg, 0.11 mmol) 116a  115b (9:1)

116a: white syrup; FT IR (neat) 3075, 2969, 2930, 2872, 1638,

1599 cm-1; 118a 1H NMR (400 MHz in CDCl3) δ 1.25-1.63 (6H, m), 2.29 (2H, m), 2.42 (3H, s),
2.97 (1H, dt, J = 2.8, 13.6 Hz), 3.76 (1H, dd, J = 3.6, 13.6 Hz), 4.10 (1H, br q, J = 6.4 Hz), 5.02
(1H, br d, J = 10.4 Hz), 5.03 (1H, br d, J = 18.0 Hz), 5.70 (1H, ddt, J = 7.2, 10.4, 18.0 Hz), 7.27
(2H, d, J = 6.8 Hz), 7.72 (2H, d, J = 6.8 Hz); 13C NMR (75 MHz in CDCl3) δ 18.37, 21.72,
24.75, 26.78, 34.17, 40.95, 52.66, 117.27, 127.16, 129.84, 135.17, 138.91, 143.09; HRMS (CI)m/z calcd for C15H22NO2S [M+H]+ 280.1371, found 280.1383.
83115a: white powder; FT IR (neat) 3028, 2939, 2858, 1598 cm-1; 1H NMR (300 MHz in CDCl3)
δ 1.39-1.69 (6H, m), 1.57 (3H, dt, J = 1.5, 6.6Hz), 2.41 (3H, s), 2.92 (1H, dt, J = 3.0, 12.0 Hz),3.67 (1H, br d, J = 12.0 Hz), 4.54 (1H, m), 5.33 (1H, ddq, J = 1.5, 6.6, 15.3 Hz), 5.56 (1H, ddq,
J = 1.5, 6.6, 15.3 Hz), 7.26 (2H, br d, J = 8.4 Hz), 7.65 (2H, br d, J = 8.4 Hz); 13C NMR (100MHz in CDCl3) δ 17.72, 18.97, 21.46, 25.12, 30.44, 41.61, 54.78, 127.26, 127.44, 128.23,
129.22, 137.63, 142.69; MS (CI) m/z 280 (M++H); HRMS (CI) m/z calcd for C15H22O2NS(M++H) 280.1371, found 280.1375.

2-Allyl-1-(mesitylsulfonyl)piperidine (115b)

N
Mts
115b

 63 

114b (33.8 mg, 0.11 mmol)

115b (33.2 mg, 98%)

115b; FT IR (neat) 3076, 3030, 2977, 2938, 2862, 1640, 1604, 1565 cm-1; 1H NMR (300
MHz in CDCl3)1.60 (4H, m), 1.69 (2H, m), 2.29 (3H, s), 2.44 (2H, m), 2.60 (6H, s), 3.00
(1H, dt, J = 13.2, 2.4 Hz), 3.46 (1H, br d, J = 13.2 Hz), 3.84 (1H, m), 4.94 (1H, br d, J = 10.2
Hz), 5.01 (1H, br d, J = 16.8 Hz), 5.52 (1H, ddt, J = 16.8, 10.2, 7.2 Hz), 6.92 (2H, s); 13C NMR(75 MHz in CDCl3)18.55, 21.01, 22.86, 25.30, 26.59, 34.07, 40.13, 51.98, 117.11, 131.82,
133.33, 134.98, 140.15, 142.06; HRMS (CI) m/z calcd for C17H26NO2S [M+H]+ 308.1684,
found 308.1679.

2-Allyl-1-(mesitylsulfonyl)-5,5-dimethylpiperidine (115c)

N
Mts
115c

 63 

114c (33.5 mg, 0.1 mmol)

115c (33.2 mg, >99%)

115c: colorless syrup; FT IR (neat) 3076, 3023, 2976, 2942, 2861, 1641, 1604, 1566
cm-1; 1H NMR (300 MHz in CDCl3) δ 0.76 (3H, s), 0.88 (3H, s), 1.25 (1H, m), 1.47 (2H, m),84

1.88 (1H, tt, J = 4.5, 14.1 Hz), 2.23 (1H, m), 2.29 (3H, s), 2.40 (1H, m), 2.59 (6H, s), 2.81 (1H,d, J = 12.9 Hz), 3.00 (1H, dd, J = 1.5, 12.9 Hz), 3.87 (1H, m), 4.91 (1H, br d, J = 11.4 Hz), 4.96
(1H, br d, J = 17.4 Hz), 5.47 (1H, m), 6.91 (2H, s); 13C NMR (75 MHz in CDCl3) δ 20.95,
22.79, 22.92, 23.18, 29.16, 30.31, 31.85, 33.52, 51.27, 51.57, 117.14, 131.74, 133.56, 134.82,
139.83, 141.93; HRMS (CI) m/z calcd for C19H30NO2S [M+H]+ 336.1997, found 336.2005.

2-Allyl-1-(mesitylsulfonyl)-1,2,3,4-tetrahydroquinoline (115d)

N
Mts
115d

 63 



114d (35.5 mg, 0.1 mmol) 115d (34.4 mg, 97%)115d: colorless syrup; FT IR (neat) 3075, 3028, 2972, 2928, 2852, 1641, 1603 cm-1; 1H
NMR (500 MHz in CDCl3) δ 1.65 (1H, m), 2.02 (1H, m), 2.12 (1H, dt, J = 8.0, 14.0 Hz), 2.30
(3H, s), 2.33 (1H, m), 2.46 (6H, s), 2.64 (2H, m), 4.20 (1H, m), 4.98 (1H, br d, J = 17.5 Hz),4.99 (1H, br d, J = 10.5 Hz), 5.69 (1H, ddt, J = 7.0, 10.5 Hz), 6.92 (2H, s), 7.07 (1H, m), 7.08
(2H, br s), 7.19 (1H, m); 13C NMR (125 MHz in CDCl3) δ 21.01, 23.21, 23.38, 25.35, 29.72,
37.61, 53.08, 117.57, 125.28, 126.26, 126.67, 128.80, 132.12, 134.35, 135.79, 140.32, 142.59;
HRMS (CI) m/z calcd for C21H26NO2S [M+H]+ 356.1684, found 356.1678.

1-Allyl-6,8-dimethoxy-1,2,3,4-tetrahydronaphthalene (118a)(E)-6,8-Dimethoxy-1-(prop-1-enyl)-1,2,3,4-tetrahydronaphthalene (119a)

OMe
MeO

118a

 63 

OMe
MeO

119a



(93:7, 34.4 mg, 97%)

117a (23.2 mg, 0.1 mmol) 118a  119a 118a: colorless syrup; FT IR (neat) 3072, 2995, 2933, 2857, 2835,

1637, 1606, 1593 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.50-1.84 (3H, m), 1.90 (1H, m), 2.06
85

(1H, m), 2.46 (1H, m), 2.70 (2H, m), 2.98 (1H, m), 3.77 (3H, s), 3.79 (3H, s), 5.00 (1H, br d, J
= 10.5 Hz), 5.01 (1H, br d, J = 16.8 Hz), 5.86 (1H, dddd, J = 5,1, 8.7, 10.5, 16.8 Hz), 6.21 (1H,d, J = 2.7 Hz), 6.28 (1H, d, J = 2.7 Hz); 13C NMR (75 MHz in CDCl3) δ 17.88, 25.42, 30.07,
31.19, 38.66, 55.21, 96.15, 104.22, 115.24, 122.31, 138.60, 158.20, 158.27; MS (CI) m/z 233(M++H); HRMS (CI) m/z calcd for C15H21O2 (M++H) 233.1542, found 233.1547.
119a: colorless syrup. FT IR (neat) 2995, 2931, 2853, 2836, 1605, 1593 cm-1; 1H NMR (500
MHz in CDCl3) δ 1.62 (3H, br d, J = 6.5 Hz), 1.64-1.73 (2H, m), 1.75-1.84 (2H, m), 2.70 (2H,m), 3.60 (1H, br s), 3.75 (3H, s), 3.78 (3H, s), 5.10 (1H, ddq, J = 15.0, 6.5, 1.5 Hz), 5.52 (1H,
ddq, J = 15.0, 6.0, 1.5 Hz), 6.23 (1H, br s), 6.28 (1H, br d, J = 2.0 Hz); 13C NMR (125 MHz in
CDCl3) δ 18.00, 18.03, 28.66, 29.86, 34.10, 55.19, 55.44, 96.23, 104.32, 120.47, 124.07,
134.91, 138.72, 158.38, 158.51; MS (CI) m/z 232 (M+); HRMS (CI) m/z calcd for C15H20O2(M+) 232.1464, found 232.1462.

Dimethyl-4-allyl-5,7-dimethoxy-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate (118b)
MeO2C

CO2Me

OMe
MeO

118b

 63 



117b (38.7 mg, 0.1 mmol) 118b (37.9 mg, 98%)118b: colorless syrup; FT IR (neat) 3072, 2999, 2953, 2839, 1739 cm-1; 1H NMR (300 MHz
in CDCl3) δ 1.95 (1H, dd, J = 7.2, 13.5 Hz), 2.19 (1H, m), 2.55 (2H, m), 3.14 (2H, br s), 3.27
(1H, ddt, J = 3.0, 7.8, 8.4 Hz), 3.58 (3H, s), 3.74 (3H, s), 3.76 (3H, s), 3.77 (3H, s), 4.99 (1H, br
d, J = 10.2 Hz), 5.01 (1H, br d, J = 17.1 Hz), 5.69 (1H, ddt, J = 6.9, 10.2, 17.1 Hz), 6.23 (1H, d,
J = 2.7 Hz), 6.28 (1H, d, J = 2.7 Hz); 13C NMR (75 MHz in CDCl3) δ 31.04, 33.91, 36.26,
39.47, 52.54, 52.75, 54.03, 55.11, 55.19, 97.04, 104.30, 116.36, 119.24, 135.96, 136.76, 158.28,
158.55, 171.16, 172.61; HRMS (CI) m/z calcd for C19H24O6 [M]+ 348.1573, found 348.1582.

86

4-Allyl-5,7-dimethoxy-2-tosyl-1,2,3,4-tetrahydroisoquinoline (118c)
TsN

OMe
MeO
118c

 63 



117c (38.7 mg, 0.1 mmol) 118c (37.9 mg, 98%)118c: colorless syrup; FT IR (neat) 3073, 2999, 2938, 2922, 2841, 2254, 1638, 1612 cm-1;
1

H NMR (300 MHz in CDCl3) δ 2.36 (1H, m), 2.43 (3H, s), 2.44 (1H, dd, J = 3.3, 9.9 Hz), 3.66

(1H, d, J = 15.6 Hz), 3.75 (3H, s), 3.79 (3H, s), 3.96 (1H, d, J = 11.4 Hz), 4.61 (1H, d, J = 15.6
Hz), 5.13 (1H, br d, J = 9.9 Hz), 5.19 (1H, br d, J = 17.1 Hz), 5.92 (1H, ddt, J = 6.9, 9.9, 17.1
Hz), 6.14 (1H, d, J = 2.1 Hz), 6.30 (1H, d, J = 2.1 Hz), 7.34 (2H, d, J = 8.1 Hz), 7.73 (2H, d, J =8.1 Hz); 13C NMR (75 MHz in CDCl3) δ 21.54, 33.11, 37.06, 45.83, 47.80, 55.33, 97.04, 101.17,
117.30, 118.89, 127.80, 129.63, 132.86, 132.91, 136.71, 143.54, 157.88, 159.06; HRMS (CI)m/z calcd for C21H26NO4S [M+H]+ 388.1583, found 388.1581.

87

32 $=<ICP-MS 7)
ICP-MS7)

'-74)&.#>HPLC

Sannac4>HPLC/":ICP-MS(86

Fig. S11>

HPLC conditions

ICP-MS Conditions

Mobile phase (A+B)

PF power …………………..1600 W

A = L-Cystein (500 mg/mL)

Carrier gas flow rate …....0.54 L/min

L-Cystein·HCl·H2O (500 mg/mL)  pH = 2.3 with HCl aq. (The solution

Make-up gas flow rate ..… 0.1 L/min
Option gas (20% O2 in Ar) ……...9%was prepared with 18 MΩ?cm water.)Spray chamber temperature…. –5 °C

B = Methanol

Sampling depth …………… 8.0 mm

Injection volume = 50 µL (0.1-0.5 mg/mL)

Fig. S1.

*+!

0%,;95

HgCl
P

HgOTf
P

148

:(

66

88

t-BuLi (,9"9gb; 1.59

m-6'.49(576 mg4.0 mmol) THF (10 mL)gb
dCcHj 0 °C

M5.0 mL, 8 mmol)-78℃

30 A~VU

[

(3-3

:%*8(6)$51$49(0.78 mL4.0 mmol) THF (15 mL)gb 0 °C
Hj

C0 °C

10 A~VUP-78 °C

0.005 M HgC12/THF gb (800 mL)C 0 °C:":

gL [dC

2 M HCl (440 mL)Nf
PThNf

GR\e

?E

>O?EfO
10 A~VUTEOS (4.4 mL, 20 mmol)

100 °C

400 rpm VUzO

t(1.0 μm)mmL), |}#6(400 mL)CH2Cl2 (400 mL)

c

'/7

EtOH (40 mL)
W~VU

ouJ=sMvn](400_a{

qr<i

148 (2.65 g)Q

66 `SD^
148 (100 mg, 0.22 mmol) CH2Cl2 (6 mL)Thb

AgOTf (114 mg, 0.44 mmol)Nf

CPfO

20 A~VU [t(1.0 μm)m

sM$69(10 mL x3)_aAgOTf F

_aqr<i66 QouJ=

PCH2Cl2 (10 mL x3)

lDB=yw(E)-3-(Hepta-4,6-dien-1-yl)-1-tosyl-1H-indole (117d)

NTs
117d

56

)&6-!)9%(1.0 g4.2 mmol) THF (7 mL0.3 M)-78℃

n-BuLi (+9gb 1.6 M2.6 mL4.2 mmol)C

gx,

cHj-78℃

30

A~VU4-(1-tosyl-1H-indol-3-yl)butanal24) (720 mg2.1 mmol) THF gb-78℃
cHj

C Nf

8 X~VUPGRjKD92&0]gb

 YZpKD92&0]gb(×2)IK]
89_a [@kYZJ MgSO4'FSB/ELS-3;C"#$!&(%:AcOEt = 10:1) KN 117d 2(307 mgS40R)T117d: white powder; FT IR(neat) 3019, 3083, 3063, 3034, 3006, 2928, 2856, 2535, 1914, 1798, 1738, 1599 cm-1; 1H NMR(300 MHz in CDCl3) δ 1.76 (2H, quin. J = 7.2 Hz), 2.62 (2H, q, J = 7.2 Hz), 2.27 (3H, s), 2.64
(2H, t, J = 7.2 Hz), 4.96 (1H, d, J = 9.8 Hz), 5.09 (1H, d, J = 17.4 Hz), 5.89 (1H, dt, J = 7.2Hz,
15.3 Hz), 6.04 (1H, br dd, J = 10.5 Hz, 15,3 Hz), 6.30 (1H, dt, J = 8.4 Hz, 16.8 Hz), 7.14 (2H,
br d, J = 8.4 Hz), 7.28 (1H, br t, J = 7.2 Hz), 7.30 (1H, s), 7.44 (1H, d, J = 7.2 Hz), 7.71 (2H, d,
J = 8.4 Hz), 7.98 (1H, d, J = 8.1 Hz); 13C NMR (75 MHz in CDCl3) δ 21.4, 24.3, 28.2, 32.0,
113.8, 115.1, 119.4, 122.9, 123.1, 124.5, 122.6, 122.6, 126.6, 129.7, 131.0, 131.5, 134.3, 135.2,
135.3, 137.1, 144.6; HRMS (CI+) m/z calcd for C22H23NO2S [M]+ 365.1450, found 365.1451.

1-[(3E,8E)-4,8-Dimethylundeca-3,8,10-trien-1-yl]-3,5-dimethoxybenzene (117e)
MeO

OMe

(E :Z = 5:1)
117e(2E)-3,7-Dimethyldeca-2,7,9-trien-1-yl acetate24) (476 mgS2.14 mmol) THF (2.2 mL)
S0 ℃

Li2CuCl4

0.1 M THF D?(0.43 mmolS4.3 mL)A+T@.G 0 ℃

15 *P65S(3,5-
48.2 mL)D? 0 ℃

%#)0,

+T0 ℃

HT89G Et2O
T:

DO

0.2 M Et2O (9.53 mmolS

2 7P651S-3G 1 M HCl <D?

4)S1 M HCl <D?(×2)SMI<(×2)

S89J MgSO4

Q0<

(

=>

'FSB/ELS;C"#$!&(%UAcOEt = 40U1)

KN 117e (659 mgS98R)2T117e: white

powder; FT IR (neat) 2999, 2931, 2854, 2835, 1593 cm-1; 1H NMR (400 MHz in CDCl3) δ1.51(2H, m), 1.57 (3H, s), 1.75 (3H, s), 1.97 (4H, m), 2.30 (2H, q, J = 7.6 Hz), 2.58 (2H, t, J = 7.6
Hz), 3.76 (6H, s), 4.97 (1H, dd, J = 1.4 Hz, 10.4 Hz), 5.09 (1H, dd, J = 1.4 Hz, 16.8 Hz), 5.17
(1H, m), 5.83 (1H, d, J = 10.4 Hz), 6.30 (1H, t, J = 2.4 Hz), 6.36 (2H, d, J = 2.4 Hz), 6.58 (1H,
dt, J = 10.4 Hz, 16.8 Hz); 13C NMR (100 MHz in CDCl3) δ 15.9, 16.6, 26.1, 29.7, 36.4, 39.3,
90

39.4, 55.3, 97.7, 106.5, 114.5, 123.8, 125.4, 133.5, 135.7, 139.8, 144.8, 160.7; HRMS (CI+) m/z
calcd for C21H31O2 [M+H]+; 315.2324, found 315.2326.

2-Allyl-1-(mesitylsulfonyl)pyrrolidine (108e)
NHMts
108e

 108a (E)-Hepta-4,6-dien-1-amine (100 mg, 0.8 mmol)

2,4,6-trimethylbenzenesulfonyl chloride (MtsCl) (210 mg, 1.0 mmol) 108e (227 mg, 92%)
108e: white powder; FT IR (neat) 3313, 3084, 3028, 2972, 2937, 2858, 1604, 1565
cm-1; 1H NMR (300 MHz in CDCl3) δ 1.53 (2H, m), 2.03 (2H, q, J = 7.2 Hz), 2.28, (3H, s),2.61 (6H, s), 2.88 (2H, q, J = 6.6 Hz), 4.47 (NH, br t, 6.0 Hz), 4.94 (1H, d, J = 10.3 Hz), 5.01
(1H, d, J = 16,8 Hz), 5.52 (1H, dt, J = 7.2 Hz, 15 Hz), 5.93 (1H, br dd, J = 10.3 Hz, 16,8 Hz),6.22 (1H, dt, J = 10.3 Hz, 16.8 Hz), 6.94 (2H, s); 13C NMR (75 MHz in CDCl3) δ 21.0, 23.0,
29.0, 29.5, 42.0, 115.6, 132.0, 133.2, 133.6, 136.8, 139.1,142.2; HRMS (CI+) m/z calcd for
C16H24NO2S [M+H]+; 294.1528, found 294.1528.

N-(2,2-Dimethyloct-7-en-1-yl)-4-methylbenzenesulfonamide (114e)

NH
Ts
114e

 108a mmol) 114e (305 mg, 78%)(E)-2,2-Dimethylocta-5,7-dien-1-amine (189 mg, 1.5
114e: white powder; FT IR (neat) 3283, 2916, 2870,

1650, 1598 cm-1; 1H NMR (500 MHz in CDCl3) δ 0.85 (6H, s), 1.28 (2H, t, J = 8.5 Hz), 1.96
(2H, dt, J = 7.0 Hz, 8.5 Hz), 2.43 (3H, s), 2.69 (2H, d, J = 7.0 Hz), 4.42 (NH, br t, 6.0 Hz), 4.96
(1H, J = 10 Hz), 5.08 (1H, d, J = 17 Hz), 5.62 (1H, dt, J = 6.5 Hz, 15 Hz), 6.01 (1H, dd, J =10.5 Hz, 15 Hz), 6.28 (1H, dt, J = 10.5 Hz, 17 Hz), 7.31 (2H, d, J = 8.0 Hz), 7.74 (2H, d, J =8.0 Hz); 13C NMR (75 MHz in CDCl3) δ 21.5, 24.8, 26.9, 33.8, 38.7, 52.7, 115.0, 127.1, 129.7,
131.0, 135.0, 136.9, 137.1, 143.4,; HRMS (CI+) m/z calcd for C17H25NO2S [M]+; 307.1606,
91

found 307.1608.

(E)-N-[2-(4-Hydroxybut-2-enyl)phenyl]-4-methylbenzenesulfonamide (65)

OH

NHTs

65



 16b 65: white powder; FTIR (neat) 3504, 3277,

3064, 3032, 2924, 2870, 1597 cm-1; 1H NMR (500 MHz in CDCl3) δ 2.40 (3H, s), 3.05 (2H, d, J
= 6.0 Hz), 4.11 (2H, br s), 5.55 (1H, dt, J = 5.5, 15.5 Hz), 5.69 (1H, dt, J = 15.5, 6.0 Hz), 6.49
(NH, br s), 7.11 (2H, m), 7.19 (1H, t, J = 7.5 Hz), 7.24 (2H, d, J = 8.0 Hz), 7.34 (1H, d, J = 8.0Hz), 7.61 (2H, d, J = 8.5 Hz); 13C NMR (125 MHz in CDCl3) δ 21.58, 34.55, 63.05, 124.57,
126.40, 127.13, 127.74, 129.14, 129.67, 130.50, 131.47, 132.42, 134.79, 136.73, 143.89;
HRMS (CI+) calcd for C17H19O3NS [M+H]+; 317.1086, found 317.1086.

(Z)-N-(2-(4-Hydroxy-2-methylbut-2-en-1-yl)phenyl)-4-methylbenzenesulfonamide (149a)
OH
NHTs



149a

16b





149a: white powder; FT IR (neat) 3500, 2920,

2253cm-1; 1H NMR (300 MHz in CDCl3) δ 1.92 (OH, br s), 2.39 (3H, s), 2.99 (2H, s), 4.16 (2H,d, J = 6.3 Hz), 5.34 (1H, dt, J = 1.2, 6.6 Hz), 6.86 (1H, s), 7.14 (6H, m), 7.39 (1H, d, J = 8.1
Hz), 7.61 (2H, d, J = 8.4 Hz), 7.67 (1H, d, J = 8.0 Hz), 7.71 (2H, d, J = 9.5 Hz); 13C NMR (125
MHz in CDCl3) δ 16.35, 21.58, 42.09, 58.98, 124.12, 126.00, 126.17, 127.05, 127.76, 129.64,
131.14, 132.22, 135.43, 136.81, 137.34, 143.83; HRMS (CI+) m/z calcd for C18H21NO3S [M]+;331.1242 found 331.1235.

(E)-6-(Tosylamino)hex-2-en-1-ol (149b)

NHTs

OH
149b



 16b 149b: colorless syrup; FT IR (neat) 3493,
923272, 2932, 2863, 1597 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.54 (2H, tt, J = 6.9, 7.9 Hz),2.02 (2H, dt, J = 5.4, 6.9 Hz), 2.41(3H, s), 2.91(2H, dt, J = 6.2, 6.9 Hz), 4.03 (2H, br s), 4.50
(1H, t, J = 6.2 Hz, NH), 5.54 (2H, m), 7.28 (2H, d, J = 8.2 Hz), 7.72 (2H, d, J = 7.6 Hz); 13C
NMR (75 MHz in CDCl3) δ 21.5, 28.9, 29.1, 42.6, 63.5, 127.1, 129.8, 130.3, 131.3, 137.0,
143.5; HRMS (CI+) calcd for C13H20NO3S [M+H]+; 270.1164, found 270.1159.

(E)-N-(7-Hydroxyhept-5-en-1-yl)-4-methylbenzenesulfonamide (149c)

NHTs



OH
149c

 16b 149c: colorless syrup; FT IR (neat) 3280,

2933, 2855 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.48 (4H, m), 1.99 (2H, dd, J = 6.3, 11.1 Hz),2.43 (3H, s), 2.94 (2H, dd, J = 6.6, 13.5 Hz), 3.59 (OH, t, J = 6.0 Hz) 4.06 (2H, d, J = 2.7 Hz),4.79 (NH, br s), 5.60 (2H, m), 7.30 (2H, d, J = 6.6 Hz), 7.74 (2H, d, J = 6.6 Hz); 13C NMR (75MHz in CDCl3) δ 21.54, 28.9, 31.5, 31.94, 42.99, 63.6, 127.1, 129.6, 129.7, 132.2, 136.9,
143.4; HRMS (CI+) calcd for C14H22NO3S [M+H]+; 284.1320, found 284.1316.

(E)-6-(3,5-Dimethoxyphenyl)hex-2-en-1-ol (149d)

OH
MeO
149d

OMe



 16a 149d: colorless syrup; FT IR (neat) 3389,

2999, 2934, 2857, 2838, 1598 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.71 (2H, m), 2.09 (2H, dt,
J = 6.6, 7.8 Hz), 2.56 (2H, t, J = 7.5 Hz), 3.78 (6H, s), 4.09 (2H, t, J = 5.4 Hz), 5.68 (2H, m),
6.30 (1H, t, J = 2.1 Hz), 6.34 (2H, br d, J = 6.1 Hz); 13C NMR (75 MHz in CDCl3) δ 30.82,
31.99, 35.89, 55.40, 63.58, 97.91, 106.77, 129.81, 132.46, 145.01, 160.92; HRMS (CI+) m/z
calcd for C14H20O3 [M]+ 236.1412, found 236.1408.

(E)-6-(3-Methoxyphenyl)hex-2-en-1-ol (149e)
93

OH
149e

MeO

,S<L 16a/@9[

5WU_149e: colorless syrup; FT IR (neat) 3358,

3028, 2999, 2932, 2857, 2839, 1924, 1842, 1731, 1669, 1602, 1584 cm-1; 1H NMR (300 MHz in
CDCl3) δ 1.25 (OH, t, J = 7.8 Hz), 1.72 (2H, m), 2.09 (2H, dt, J = 6.9, 7.7 Hz), 2.60 (2H, t, J =7.7 Hz), 3.80 (3H, s), 4.10 (2H, t, J = 7.8 Hz), 5.68 (2H, m), 6.75 (3H, m), 7.20 (1H, dd, J = 7.4,
8.8 Hz); 13C NMR (75 MHz in CDCl3) δ 30.55, 31.62, 35.28, 54.98, 63.43, 110.83, 114.12,
120.77, 129.09, 129.31, 132.40, 143.83, 159.42; HRMS (CI+) m/z calcd for C13H18O2 [M+]206.1307, found 206.1302.

(E)-6-(1-Tosyl-1H-indol-2-yl)hex-2-en-1-ol (149f)

OH
TsN
149f

,S<L 16a/@9[

5WU_149f: colorless syrup; FT IR (neat) 3369,

3046, 2931, 2864, 1596, 1567 cm-1; 1H NMR (300 MHz in CDCl3) δ1.86 (2H, m), 2.18 (2H, dt,
J = 7.4, 8.0 Hz), 2.33 (3H, s), 3.00 (2H, br t, J = 7.4 Hz), 4.10 (2H, br d, J = 4.3 Hz), 5.71 (2H,m), 6.38 (1H, br s), 7.16-7.28 (4H, m), 7.41 (1H, ddd, J = 0.6, 1.2, 7.8 Hz), 7.60 (2H, d, J = 8.4
Hz), 8.16 (1H, br d, J = 8.1 Hz); 13C NMR (75 MHz in CDCl3) δ 21.52, 28.29, 28.40, 31.68,
63.68, 108.91, 114.80, 120.06, 123.48, 123.85, 126.21, 129.70, 129.77, 132.35, 136.05, 137.16,
141.90, 144.65; HRMS (CI+) m/z calcd for C21H23O3NS [M+] 369.1399, found 369.1394.

M*%

.8

2>9[`

"Z0B$^4G

M*(\%(0.3-0.6mmol)

66 (20 mol])). D.K
-7

RJ TLC &?

TP^AF

##O 280 rpm

'=^V3IX
!#94

CH2Cl2 HC(0.15 M);:.

Y+. ICE1$

QUN8K6.

1-Allyl-6,8-dimethoxy-1,2,3,4-tetrahydronaphthalene (118a)
117a (93.2 mg0.401 mmol) CH2Cl2 (7 mL0.3 M)e}
mmolHg 16.04 mgnO)
66

HC

?cNVUT

_

aIgy

BR]b

118a

66

66h_8^k;NBR

W>ot8{m
.`Dj

BR]b

AJG:=YdK
Hg(0)

j(^f

dK

.Qh_64q61p31e_(2 mL)M

10SnCl2e_k9

Table S1s

0.0790.237 ng^Q(87.4 mg0.376 mmol, 94%)\117a

115 ℃30=\140 ℃30=?iμL) {l^5 mLM

x

(2"&3$40,%1-!6(.

#'5AcOEt = 101)w|

, Lc66 (36.0 mg0.08

FXZ<

Q`Dj(20e_5 mL)^FX

0.0160.047 ppbnO.

_866]lf)<0.001.

Table S1

Dimethyl-4-allyl-5,7-dimethoxy-3,4-dihydronaphthalene-2,2(1H)-dicarboxylate (118b)@Dj118aE[SP117b (140 mg, 0.4 mmol)118b (123 mg, 0.351
mmol)
1Q_866]lj(^H,13C-NMR)/$,3+6*v7u|f)<0.001.

@Dj7z

4-Allyl-5,7-dimethoxy-2-tosyl-1,2,3,4-tetrahydroisoquinoline (118c)
95





r~



)118a$#3!5117c (155 mg, 0.4 mmol)118c (133 mg, 0.343mmol)"65'
1

H,13C-NMR

66%*)(

5-,&2

1/)

()

<0.0014.

.

+06

1-Allyl-9-tosyl-2,3,4,9-tetrahydro-1H-carbazole (118d)

NTs
118d

)118a$#3!5117d (110 mg, 0.3 mmol)118d (101 mg, 0.276mmol)"65'66%*)(

&2()<0.0014.

118d: white powder; FT IR (neat) 3071, 3032, 3000, 2933, 2855, 1911, 1731, 1683, 1638, 1598
cm-1; 1H NMR (500 MHz in CDCl3) δ 1.67-1.82 (3H, m), 2.03 (1H, m), 2.18 (1H, m), 2.29 (3H,s), 2.46 (1H, m), 2.67 (1H, dt, J = 3.5 Hz, 12 Hz), 2.90 (1H, m), 3.44 (1H, dt, J = 2.5 Hz, 8.0
Hz), 5.09 (2H, br t, J = 10 Hz, 18 Hz), 5.94 (1H, m), 7.11 (2H, d, J = 8.0 Hz), 7.21 (1H, dt, J =1.0 Hz, 7.5 Hz), 7.26 (1H, dt, J = 1.5 Hz, 7.5 Hz), 7.30 (1H, dd, J = 1.0 Hz, 7.5 Hz), 7.52 (1H, d,
J = 8.0 Hz), 8.14 (1H, d, J = 8.0 Hz); 13C NMR (125 MHz in CDCl3) δ 17.1, 21.1, 21.5, 26.0,
33.6, 39.2, 115.4, 116.4, 118.2, 119.9, 123.6, 124.2, 126.2, 129.6, 130.8, 135.5, 136.1, 137.3,
139.4, 144.3; HRMS (CI+) m/z calcd for C22H24NO2S [M+H]+ 366.1528, found 366.1530.

(±)-(1S,4aS,10aS)-1-Allyl-5,7-dimethoxy-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydrophena
nthrene (118e)(±)-(1S,4aS,10aS)-5,7-Dimethoxy-1,4a-dimethyl-1-[(E)-prop-1-en-1-yl]-1,2,3,4,4a,9,10,10aoctahydrophenanthrene (119e)
MeO

OMe

H

MeO

OMe

H

118e

119e

96



* 118a

mmol)

!%

$4

"6117e (100 mg, 0.318 mmol) 118e (67.2 mg, 0.213

119e (11.4 mg, 0.036 mmol)#76(66&+*(

'3))<0.00157118e: colorless syrup; FT IR (neat) 3071, 2944, 2924, 2856, 1636
cm-1; 1H NMR (500 MHz in CDCl3) δ 0.93 (3H, s), 1.11 (1H, dt, J = 3.0 Hz, 13.0 Hz), 1.29 (3H,s), 1.31-1.24 (3H, m), 1.59-1.46 (1H, m), 1.78-1.66 (3H, m), 1.94 (1H, dd, J = 7.0 Hz, 13.5 Hz),2.15 (1H, dd, J = 8.0 Hz, 13.5 Hz), 2.74-2.87 (2H, m), 3.05 (1H, dt, J = 3.5 Hz, 13.0 Hz), 3.75
(6H, s), 5.01 (2H, m), 5.82 (1H, m), 6.18 (1H, d, J = 2.5 Hz), 6.27 (1H, d, J = 2.5 Hz); 13C
NMR (150 MHz in CDCl3) δ 18.5, 19.1, 20.4, 21.6, 33.0, 36.5, 36.9, 37.0, 39.2, 48.9, 49.9, 55.0,
55.1, 97.6, 104.8, 116.9, 130.4, 135.5, 138.8, 157.8, 159.6; HRMS (CI+) m/z calcd for C21H30O2[M]+; 314.2246, found 314.2231. 119e; colorless syrup; FT IR (neat) 3155, 2953, 2929, 2857,
1793 cm-1; 1H NMR (600 MHz in CDCl3) δ 0.99 (3H, s), 1.18 (1H, m), 1.20 (3H, s), 1.34 (1H,m), 1.45 (2H, m), 1.59 (1H, m), 1.68 (3H, dd, J = 1.8 Hz, 12.0 Hz), 1.79-1.70 (1H, m), 1.86 (1H,
dd, J = 6.0 Hz, 12.6 Hz), 1.91 (1H, dd, J = 1.8 Hz, 12.6 Hz), 2.84 (2H, m), 3.05 (1H, dt, J = 2.4
Hz, 13.2 Hz), 3.75 (3H, s), 3.75 (3H, s), 5.38 (1H, m), 5.56 (1H, m), 6.19 (1H, d, J = 2.4 Hz),6.27 (1H, d, J = 2.4 Hz); 13C NMR (150 MHz in CDCl3) δ 18.5, 18.8, 19.1, 19.2, 32.3, 33.7,
38.0, 36.9, 38.8, 39.3, 54.7, 55.0, 55.1, 97.6, 104.9, 119.5, 129.9, 136.9, 138.7, 157.7, 159.8;
HRMS (CI+) m/z calcd for C21H30O2 [M]+; 314.2246, found 314.2240.

2-Allyl-1-tosylpyrrolidine (63)* 118a!%$4"6117c (106 mg, 0.4 mmol) 118c (98.6 mg, 0.372&+*(

mmol)#76(66

H,13C-NMR 

6.-

1

20

'3

))

*

/

<0.0015.
,172-Allyl-1-(mesitylsulfonyl)pyrrolidine (109e)

N
Mts
109e



* 118a!%$4"6108e (160 mg, 0.545 mmol) 109e (144 mg, 0.49197mmol)#76(66&+*(

'3))<0.0015.109e:

white powder; FT IR (neat) 2974, 2939, 2873, 1639, 1604, 1565 cm-1; 1H NMR (300 MHz in
CDCl3) δ 1.69-2.05 (5H, m), 2.21 (2H, m), 2.28, (3H, s), 2.63 (6H, s), 3.10 (1H, dt, 6.0Hz, 9.9Hz), 3.36 (1H, dt, J = 7.2, 12.8 Hz), 3.87 (1H, m), 4.95 (1H, d, J = 6.4 Hz), 4.96 (1H, d, J = 9.3
Hz), 5.59 (1H, m), 6.94 (2H, s); 13C NMR (75 MHz in CDCl3) δ 21.0, 22.9, 24.2, 30.5, 39.5,
47.8, 58.5, 117.5, 131.9, 133.3, 134.6, 140.1, 142.5; HRMS (CI+) m/z calcd for C16H24NO2S[M+H]+; 294.1528 found 294.1520.

2-Allyl-1-(mesitylsulfonyl)piperidine (115b)


*118a

!%

$4

"6114b (123 mg, 0.4 mmol)115b (113 mg, 0.367mmol)#76(1

H,13C-NMR

66&+*(

6.-

'3

20

*

))

<0.0015.

/,172-Allyl-1-(mesitylsulfonyl)-5,5-dimethylpiperidine (115c)


*118a

!%

$4

"6114c (101 mg, 0.3 mmol)115c (96.9 mg, 0.288mmol)#76(1

H,13C-NMR

66&+*(

6.-

'3

20

*

))

<0.0015.

/,172-Allyl-5,5-dimethyl-1-tosylpiperidine (115e)

N
Ts
115e



* 118a!%$4"6114e (123 mg, 0.4 mmol) 115e (104 mg, 0.338mmol)#76(66&+*(

'3))<0.0015.115e:

white powder; FT IR (neat) 3076, 2951, 2863, 1640, 1599 cm-1; 1H NMR (500 MHz in CDCl3)
δ 0.88 (3H, s), 0.90 (3H, s), 1.22 (1H, dt, J = 4.5 Hz, 14 Hz), 1.31 (1H, dt, J = 3.5 Hz, 14 Hz),1.52 (1H, dt, J = 4.5 Hz, 14 Hz), 1.76 (1H, m), 1.95 (1H, dt, J = 5.0 Hz, 13.5 Hz), 2.28 (1H, dt,
98J = 9.0 Hz, 13.5 Hz), 2.41 (3H, s), 2.67 (1H, d, J = 13.0 Hz), 3.31 (1H, dd, J = 1.5 Hz, 13.0 Hz),4.05 (1H, quin., J = 5.0 Hz), 4.95 (2H, d, J = 12.5 Hz), 5.58 (1H, m), 7.27 (2H, d, J = 8.0 Hz),7.68 (2H, d, J = 8.5 Hz); 13C NMR (125 MHz in CDCl3) δ 21.5, 23.0, 23.5, 29.0, 30.4, 31.6,
32.6, 51.2, 51.9, 117.3, 127.0, 129.5, 134.9, 138.6, 142.8; HRMS (CI+) m/z calcd for
C17H26NO2S [M+H]+; 308.1684, found 308.1666.

1-(Phenylsulfonyl)-2-vinylindoline (67)

N
Ts
67

 118a !65 (95.0 mg, 0.3 mmol)
"

! 66 (





)

67 (89.7 mg, 0.3 mmol)<0.001

.67: white

powder; FTIR (neat) 3069, 3013, 2953, 2922, 2851, 1735, 1603 cm-1; 1H NMR (500 MHz in
CDCl3) δ 2.65 (1H, dd, J = 3.0 Hz, 16.5 Hz), 2.94 (1H, dd, J = 10.0, 16.5 Hz), 4.76 (1H, m),
5.16 (1H, d, J = 10.0 Hz), 5.39 (1H, d, J = 17.0 Hz), 5.91 (1H, ddd, J = 6.0, 10.0, 17.0 Hz), 7.03
(2H, m), 7.22 (1H, t, J = 7.0 Hz), 7.39 (2H, t, J = 8.0 Hz), 7.53 (1H, t, J = 7.5 Hz), 7.67 (1H, d,
J = 8.0 Hz), 7.71 (2H, d, J = 9.5 Hz); 13C NMR (125 MHz in CDCl3) δ 34.97, 63.88, 115.91,
116.89, 124.64, 125.12, 127.08, 127.87, 128.97, 131.23, 133.02, 137.44, 138.32, 141.30;
HRMS (CI+) calcd for 285.0824 [M]+; C16H15O2NS, found 285.0807.
2-Methyl-1-tosyl-2-vinylindoline (150a)

Ts

150a

118a!149a (118 mg, 0.356 mmol)
mmol).

!66(





)

150a (92.8 mg, 0.296<0.001

"150a;

white powder; FT IR (neat) 3068, 3030, 2973, 2924, 2853, 2256, 1916, 1644, 1599 cm-1; 1H
NMR (300 MHz in CDCl3) δ 1.78 (3H, s), 2.38 (3H, s), 2.96 (1H, d, J = 16.2 Hz), 3.13 (1H, d,
J = 16.2 Hz), 5.15 (1H, d, J = 10.5 Hz), 5.31 (1H, d, J = 17.1 Hz), 6.10 (1H, dd, J = 10.5 Hz,
17.1 Hz), 6.94 (1H, dt, J = 0.9 Hz, 7.2 Hz), 7.09 (1H, dd, J = 0,9 Hz, 7.5 Hz), 7.15 (1H, dt, J =99

0.6 Hz, 7.5 Hz), 7.23 (2H, d, J = 8.1 Hz), 7.51 (1H, d, J = 8.1 Hz), 7.79 (2H, d, J = 8.4 Hz); 13C
NMR (75 MHz in CDCl3) δ 21.5, 25.2, 44.8, 72.0, 113.8, 114.0, 122.8, 124.9, 127.0, 127.7,
128.6, 129.5, 138.7, 141.3, 141.8, 143.5; MS (Cl) m/z 313 [M]+; HRMS (CI+) m/z calcd for
C18H19NO2S; 313.1136 found 313.1129.

1-Tosyl-2-vinylpyrrolidine (150b)
N
Ts
150b

 118a !149a (105 mg, 0.356 mmol)
mmol)"! 66 (





150b (83.4 mg, 0.332<0.001 . 150b:)

white powder; FT IR (neat) 3133, 3028, 2915, 2865, 1596 cm-1; 1H NMR (300 MHz in CDCl3)
δ 1.59–1.85 (m, 4H), 2.43 (s, 3H), 3.24 (m, 1H), 3.44 (1H, ddd, J = 4.8, 7.6, 10.4 Hz), 4.14 (1H,m), 5.11 (1H, dd, J = 1.5, 10.4 Hz), 5.27 (1H, dd, J = 1.5, 17.2 Hz), 5.81 (1H, ddd, J = 6.2, 10.
4, 17.2 Hz), 7.30 (2H, d, J = 8.3 Hz), 7.72 (2H, d, J = 8.3 Hz); 13C NMR (300 MHz in CDCl3) δ
21.65, 23.88, 32.44, 48.91, 62.04, 115.43, 127.68, 129.70, 135.36, 138.84, 143.36; HRMS (CI+)
calcd for C13H18O2NS [M+H]+; 252.1058, found 252.1049.

1-Tosyl-2-vinylpiperidine (150c)

NTs
150c

 118a !149c (101 mg, 0.356 mmol)
mmol)" ! 66 (





)

150c (32.0 mg, 0.072<0.001 "150c:

white powder; FT IR (neat) 2925, 2857, 1732, 1597 cm-1; 1H NMR (300 MHz in CDCl3) δ
1.33–1.56 (m, 4H), 1.65 (2H, m), 2.41 (s, 3H), 2.96 (1H, m), 3.44 (1H, m), 7.66 (1H, m), 4.60
(1H, m), 5.13 (1H, dd, J = 1.5 Hz, 10.4 Hz), 5.27 (1H, dd, J = 1.5, 17.2 Hz), 5.70 (1H, ddd, J =5.2, 10.4, 17.2 Hz), 7.26 (2H, d, J = 8.3 Hz), 7.70 (2H, d, J = 8.3 Hz); 13C NMR (75 MHz in
CDCl3) δ 19.1, 21.6, 25.0, 29.7, 41.7, 55.1, 117.2, 127.4, 129.5, 135.6, 138.0, 142.9; HRMS(CI+) calcd for C14H20O2NS [M+H]+; 266.1214, found 252.1207.
100

6,8-Dimethoxy-1-vinyl-1,2,3,4-tetrahydronaphthalene (150d)

MeO
150d
OMe

" 118a &(!$(149d (84 mg, 0.356 mmol)
(69.0 mg, 0.316 mmol)) ( 66 #"(



%

)

150d

<0.001'. 150d: colorless syrup; FT IR (neat) 3076, 2996, 2937, 2866, 2835, 1633, 1610 cm-1; 1H
NMR (300 MHz in CDCl3) δ 1.66-1.89 (4H, m), 2.72 (2H, m), 3.67 (1H, m), 3.76 (3H, s), 3.78
(3H, s), 4.68 (1H, dt, J = 17.2, 1.9 Hz), 4.98 (1H, dt, J = 10.2, 1.9 Hz), 5.94 (1H, ddd, J = 17.2,
10.2, 5.6 Hz), 6.24 (1H, d, J = 2.5 Hz), 6.29 (1H, d, J = 2.5 Hz); 13C NMR (75 MHz in CDCl3)
δ 17.94, 28.08, 29.76, 35.09, 55.01, 55.20, 96.06, 104.22, 113.50, 119.23, 138.82, 142.28,
158.43, 158.48; HRMS (CI+) m/z calcd for C14H18O2 [M]+ 218.1306, found 218.1297.

6-Methoxy-1-vinyl-1,2,3,4-tetrahydronaphthalene (150e1)
8-Methoxy-1-vinyl-1,2,3,4-tetrahydronaphthalene (150e2)

OMe

MeO

150e1

150e2

" 118a &(!$(149e (73.4 mg, 0.356 mmol)
150e1 (41.6 mg, 0.221 mmol) 150e2 (5.4 mg, 0.029 mmol)) ( 66 
#"(



%

)

<0.001'. 150e1: colorless syrup; FT IR (neat) 3075, 2996,

2932, 2857, 2834, 1635, 1608, 1576 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.63-1.75 (2H, m),
1.85-1.96 (2H, m), 2.75 (2H, t, J = 5.5 Hz), 3.39 (1H, q, J = 6.6 Hz), 3.77 (3H, s), 5.01 (1H, ddd,
J = 17.6, 1.9, 1.1 Hz), 5.06 (1H, ddd, J = 10.8, 1.9, 0.8 Hz), 5.84 (1H, ddd, J = 17.6, 10.8, 8.1
Hz), 6.62 (1H, d, J = 2.6 Hz), 6.70 (1H, dd, J = 8.4, 2.6 Hz), 7.07 (1H, d, J = 8.4 Hz); 13C NMR(75 MHz in CDCl3) δ 20.74, 30.01, 30.19, 42.99, 55.16, 111.83, 113.50, 114.70, 130.31, 130.43,
138.15, 143.39, 157.66; HRMS (CI+) m/z calcd for C13H17O [M++H] 189.1279, found 189.1255.
150e2: colorless syrup; FT IR (neat) 3077, 3034, 2998, 2933, 2866, 2834, 1907, 1823, 1732,
101

1635, 1600, 1583 cm-1; 1H NMR (300 MHz in CDCl3) δ1.64-1.92 (4H, m), 2.76 (2H, m), 3.76
(1H, m), 3.78 (3H, s), 4.68 (1H, dt, J = 17.2, 1.8 Hz), 4.99 (1H, dt, J = 10.2, 1.8 Hz), 5.96 (1H,
ddd, J = 17.2, 10.2, 5.6 Hz), 6.67 (1H, br d, J = 8.2 Hz), 6.72 (1H, dd, J = 7.7, 0.7 Hz), 7.11
(1H, dd, J = 8.2, 7.7 Hz); 13C NMR (75 MHz in CDCl3) δ 17.89, 28.03, 29.31, 35.54, 55.40,
107.41, 113.80, 121.52, 126.47, 126.86, 138.47, 142.14, 157.55; HRMS (CI+) m/z calcd for
C13H17O [M++H] 189.1279, found 189.1254.

9-Tosyl-4-vinyl-2,3,4,9-tetrahydro-1H-carbazole (150f)

TsN
150f

#&@ 118a'4/I,K"?F73!K149f (127 mg, 0.356 mmol) 150f

(110 mg, 0.313 mmol)-LK8
 66 5A@(6G=)<0.001J

. 150f: white powder; FT IR (neat) 3071, 3046, 3000, 2937, 2861, 1913, 1829, 1793,

1732, 1636, 1598 cm-1; 1H NMR (300 MHz in CDCl3) δ1.67-1.91 (4H, m), 2.32 (3H, s), 2.92
(1H, dt, J = 6.3, 16.2 Hz), 3.06 (1H, dt, J = 4.8, 16.2 Hz), 3.53 (1H, dt, J = 4.5, 7.2 Hz), 4.90
(1H, ddd, J = 0.9, 1.8, 17.1 Hz), 5.05 (1H, ddd, J = 0.9, 1.8, 10.2 Hz), 5.86 (1H, ddd, J = 7.2,
10.2, 17.1 Hz), 7.13-7.26 (4H, m), 7.39 (1H, dd, J = 0.9, 7.5 Hz), 7.64 (2H, br d, J = 8.1 Hz),8.14 (1H, br d, J = 7.8 Hz); 13C NMR (75 MHz in CDCl3) δ19.79, 21.55, 24.76, 29.01, 36.80,
114.35, 115.46, 119.18, 123.05, 123.75, 126.30, 129.76, 129.98, 136.05, 136.20, 136.38, 140.68,
144.47; HRMS (CI+) m/z calcd for C21H21O2NS [M+] 351.1293, found 351.1290.

(E)-4-Methyl-N-(pent-3-en-2-yl)benzenesulfonamide (154a)
NHTs

154a

(E)-pent-3-en-2-ol (43.0 mg, 0.5 mmol) (128.4 mg, 0.75 mmol) CH2Cl2 (8mLK0.3 M)<D, *;

10KBE

66 (45.1 mg, 0.1 mmol)"L;+5 2H

66 (%L89)>CK$.5:
102

%&!$((mmol)= <3)66

'>AcOEt = 10>1)78 154a .(110 mg, 0.460
165(



29

4)

<0. 001;=154a: white

powder; FT IR (neat) 3277, 3031, 2976, 2932, 2877; 1H NMR (400MHz in CDCl3) δ 1.15 (3H,d, J = 6.8 Hz), 1.51 (3H, br d, J = 6.4 Hz), 2.42 (3H, s), 3.84 (1H, m), 4.63 (NH, br d, J = 6.8
Hz), 5.18 (1H, ddq, J = 1.6, 6.8, 15.2 Hz), 5.43 (1H, ddq, J = 1.2, 6.4, 15.2 Hz), 7.28 (2H, br d,
J = 8.0 Hz), 7.74 (2H, br d, J = 8.0 Hz); 13C NMR (100 MHz in CDCl3) δ 17.5, 21.5, 21.9, 51.4,
126.6, 127.2, 129.5, 131.8, 138.1, 143.1; HRMS (CI+) m/z cacld for C12H18NO2S [M+H]+
240.1059, found 240.1058.

Methyl (E)-pent-3-en-2-ylsulfamate (155a)
NHSO2OMe
155a*+5154a,0/:-<(E)-pent-3-en-2-ol (43.0 mg, 0.5 mmol)#%#((83.5 mg, 0.75 mmol)155a (78.0 mg, 0.435 mmol).=
165(



29

4)

<3)

66

<0.001;=155a: colorless oil; FT IR (neat) 3298, 2980,

2958 2935, 2016, 2884 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.31 (3H, d, J = 6.9 Hz), 1.70
(3H, dq, J = 0.9 Hz, 6.6 Hz), 3.82 (3H, s), 4.00 (1H, m), 4.26 (NH, br s), 5.44 (1H, m), 5.71
(1H, ddd, J = 1.2 Hz, 6.3 Hz, 15.3 Hz); 13C NMR (75 MHz in CDCl3) δ 17.6, 21.5, 52.2, 56.2,
127.4, 131.5; HRMS (CI+) m/z calcd for C6H13NO3S [M]+; 179.0616 found 179.0613.

N-(Cyclohex-2-en-1-yl)-4-methylbenzenesulfonamide (154b)
NHTs

154b

*+5154a,0/:-<cyclohex-2-en-1-ol (49.0 mg, 0.5 mmol)%"(128.4 mg, 0.75 mmol)154b (122 mg, 0.485 mmol).= <3)
(



29

4)

66

165

<0.001;. 154b: white powder; FT IR (neat) 3279, 3028, 2934,

2863, 1428, 1328 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.51-1.60 (4H, m), 1.93 (2H, quin, J =103

3.6 Hz), 2.43 (3H, s), 3.82 (1H, dd, J = 3.3, 6.3 Hz), 4.43 (NH, d, J = 8.4 Hz), 5.33 (1H, ddt, J= 2.1, 3.6, 10.2 Hz), 5.76 (1H, ddt, J = 2.1, 3.6, 10.2 Hz), 7.29 (2H, d, J = 8.7 Hz), 7.77 (2H, d,
J = 8.7 Hz); 13C NMR (75 MHz in CDCl3) δ 19.3, 21.5, 24.5, 30.3, 49.0, 127.0, 129.7, 131.6,
138.3, 143.2; HRMS (EI+) m/z calcd for C13H17NO2S [M+]; 251.0980, found 251.0981.

Methyl cyclohex-2-en-1-ylsulfamate (155b)
NHSO2OMe155b(154a#"+-(E)-pent-3-en-2-ol (49.0 mg, 0.5 mmol)

(83.5 mg, 0.75 mmol)

155b (88.0 mg, 0.46 mmol)!. -&66$

)((



%*'

)

<0.001,. 155b: colorless syrup; FT IR (neat) 3300, 3030,

2940, 2865, 2839 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.67 (3H, m), 1.99 (3H, m), 3.84 (3H,s), 3.98 (1H, m), 4.51 (NH, br d, J = 8.0 Hz), 5.68 (1H, m), 5.90 (1H, m); 13C NMR (75 MHz in
CDCl3) δ 19.2, 24.6, 29.8, 49.8, 56.3, 126.5, 132.2; HRMS (CI+) m/z calcd for C7H14NO3S[M+H]+; 192.0694, found 192.0693.

N-(Cyclopent-2-en-1-yl)-4-methylbenzenesulfonamide (154c)
NHTs
154c

(154a#"+-cyclopent-2-en-1-ol (42.0 mg, 0.5 mmol) 

(128.2 mg, 0.749 mmol)154c (92.4 mg, 0.389 mmol)!.
((



%*'

)

-&66$)<0.001,. 154c; white powder: FT IR (neat) 3276, 3061,

2927, 2854 cm-1; 1H NMR (300MHz in CDCl3) δ 1.51 (1H, m), 2.07-2.25 (2H, m), 2.36 (1H,m), 2.44 (3H, m), 4.39 (1H, m), 4.68 (NH, d, J = 9.3 Hz), 5.43 (1H, br dd, J = 2.1, 5.7 Hz), 5.85
(1H, dd, J = 2.1, 5.7 Hz), 7.31 (2H, d, J = 8.4 Hz), 7.78 (2H, d, J = 8.4 Hz); 13C NMR (75 MHz
in CDCl3) δ 21.5, 30.8, 31.5, 59.8, 127.1, 129.7, 130.4, 135.0, 138.1, 143.3; HRMS (CI+) m/z
calcd for C12H16NO2S [M+H]+; 238.0902, found 238.0887.

104

Methyl cyclopent-2-en-1-ylsulfamate (155c)
NHSO2OMe155c

(154a#"+-cyclopent-2-en-1-ol (42.0 mg, 0.5 mmol)

(128.4 mg, 0.749 mmol)
66$)((



%*'

)

155c (61.9 mg, 0.349 mmol)!.

-&

<0.001,. 155c: colorless oil; FT IR (neat) 3612,

3313, 3062, 2956, 2856 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.76 (1H, m), 2.40 (3H, m), 3.85
(3H, s), 4.39 (NH, br s), 4.52 (1H, m), 5.77 (1H, ddt, J = 1.8, 3.9, 5.7 Hz), 6.01 (1H, m); 13C
NMR (75 MHz in CDCl3) δ 30.9, 31.4, 56.3, 60.6, 130.1, 135.8; HRMS (CI+) m/z calcd for
C6H12NO3S [M+H]+ 178.0538, found 178.0539.

(E)-4-Methyl-N-(4-phenylbut-3-en-2-yl)benzenesulfonamide (154d)
NHTs
Ph

154d

(154a#"+-(E)-4-phenylbut-3-en-2-ol (44.5 mg, 0.3 mmol)

(77.0 mg, 0.45 mmol)154d (81.7 mg, 0.271 mmol)!.
$)((



%*'

)

-&66

<0.001,. 154d: white powder; FT IR (neat) 3271, 3058,

3026, 2976, 2929. 2870 cm-1; 1H NMR (400 MHz, CDCl3) δ 1.27 (3H, d, J = 6.6 Hz), 2.34 (3H,s), 4.05−4.15 (1H, m), 5.08 (1H, br s), 5.83 (1H, dd, J = 6.8, 16.0 Hz), 6.28 (1H, d, J = 16.0 Hz),7.14−7.20 (7H, m), 7.75 (2H, d, J = 8.4 Hz); 13C NMR (100 MHz, CDCl3) δ 21.4, 21.9, 51.6,
126.3, 127.2, 127.6, 128.4, 129.5, 130.1, 130.5, 136.1, 138.1, 143.3; HRMS (CI+) m/z calcd for
C12H16NO2S [M+H]+; 238.0902, found 238.0887.

(E)-Methyl (4-phenylbut-3-en-2-yl)sulfamate (155d)
NHSO2OMePh

155d( 154a #"+-(E)-4-phenylbut-3-en-2-ol (44.5 mg, 0.3 mmol)

(50.0 mg, 0.45 mmol) 155d (57.2 mg, 0.237 mmol)!. -&105-96(

66.@5)<0.001C. 155d: white powder; FT IR (neat)

3301, 3083, 3058, 3027, 2978, 2954, 2932, 2882, 1697, 1520 cm-1; 1H NMR (400 MHz in
CDCl3) δ 1.42 (3H, d, J = 6.8 Hz), 3.08 (3H, s), 4.22 (1H, m), 4.79 (NH, d, J = 7.2 Hz), 6.14
(1H, dd, J = 6.8, 16.0 Hz), 6.58 (1H, d, J = 16.0 Hz), 7.23 (2H, t, J = 7.6 Hz), 7.26 (2H, d, J =7.6 Hz), 7.36 (1H, t, J = 7.6 Hz); 13C NMR (100 MHz in CDCl3) δ 21.5, 52.4, 56.4, 126.4,
126.5, 127.6, 128.0, 128.6, 129.6, 131.1, 136.1; HRMS (CI+) m/z calcd for C11H15NO3S [M+]241.0762, found 241.0751.

2-Butyl-1-tosyl-1H-indole (67)N
Ts

n-C4H967

6 118a

,

*A

&

DN-(2-(hex-1-yn-1-yl)phenyl)-4-methylbenzenesulfo-

namide17) (164 mg, 0.5 mmol) 157 (164 mg, 0.5 mmol)'ED3
96(

.@

66

-

5)<0.001C. 157: white powder; FT IR (neat) 3051, 2958,

2930, 2871, 1596, 1454, 1376, 1218, 1179 cm-1; 1H NMR (200 MHz in CDCl3) δ 0.96 (3H, t, J
= 7.4 Hz), 1.48 (2H, m), 1.73 (2 H, quin, J = 7.4 Hz), 2.33 (3H, s), 2.98 (2H, t, J = 7.4 Hz), 6.38
(1H, s), 7.15-7.29 (4H, m), 7.40 (1H, d, J = 7.8 Hz), 7.61 (2H, d, J = 7.8 Hz), 8.16 (1H, dd, J =0.8, 7.8 Hz). 13C NMR (50 MHz in CDCl3) δ 13.88, 21.44, 22.43, 28.69, 30.95, 108.56, 114.78,
120.00, 123.41, 123.71, 126.19, 129.71, 129.84, 136.22, 137.19, 142.49, 144.54; HRMS (EI+)
calcd for C19H21NO2S [M+] 327.1293, found 327.1283.

81)

+>66(44.9 mg, 20 mol%)8 65 (159 mgD
0.5 mmol) 67 
,

*A

&

20 !;?. 1)%(159 mgD0.5 mmol)8
66

50 molC

7(D6 118a

((2123 !:1) 66 8

021)/F2 M HCl 43(30 mL)
106

#B)

D65

<.

D8=" 66 (220 mg)$"/

%#-/!

% 280 rpm  1 .0/ )+&(60 mLx2)/MeOH (50 mL)/Et2O (50 mL)mL),*/P2O5 '($.

107

CH2Cl2 (50Z1Y ;fd
TBDPS .,-0"-3_^(E)-tert-Butyldiphenyl(undec-6-en-5-yloxy)silane (182b)
OTBDPS
n-C4H9n-C4H9182b(E)-undec-6-en-5-ol75) (670 mg, 3.93 mmol)DMF (13 mL)PL
mmol)

)

0- (803 mg, 11.8 mmol)0 °C]VKM6

, TBDPSCl (1.2 mL, 4.72

6h<O

2EcDC.

8@4IhFHU'//ab!-(4:1)

B5iF

HWSKXb($*

2ThR`=Q\i?JN,-+*.(#+&0 ('//AcOEt 50:1) [^

182b (244 mg, 83g)?

i182b: colorless syrup; FT IR (neat) cm-1; 3071, 3049, 2997, 2958, 2932, 2895, 2858; 1H
NMR (300 MHz in CDCl3) δ 0.83 (6H, m), 1.04 (9H, m), 1.25 (8H, m), 1.52 (2H, m), 1.86 (2H,q, J = 6.6 Hz), 4.04 (1H, q, J = 7.2 Hz), 5.23 (1H, dt, J = 6.6 Hz, 15.3 Hz), 5.36 (1H, ddt, J =1.2 Hz, 7.2 Hz, 15.3 Hz), 7.30-7.44 (6H, m), 7.64-7.70 (4H, m); 13C NMR (75 MHz in CDCl3)
δ 13.99, 14.10, 19.37, 22.19, 22.62, 27.11, 31.31, 31.79, 37.85, 74.77, 127.20, 127.37, 129.25,
129.38, 131.18, 132.82, 134.70, 134.76, 135.95, 136.06; HRMS (CI+) m/z calcd for C27H39OSi[M-H]+ 407.2770 found 407.2669.

tert-Butyl(2-cyclohexen-1-yloxy)diphenylsilane (186)OTBDPS

186

79U 182b:GAe>h2-.'%0- (250 mg, 2.45 mmol) 186(840 mg, 1.12 mmol, 98%)?i186: colorless syrup; FT IR (neat) 3070, 3048, 3027, 2998,
2931, 2892, 2858, 1956, 1888, 1822 cm-1; 1H NMR (300 MHz in CDCl3) δ 1.08 (9H, s),
1.36-1.49 (2H, m), 1.58-1.78 (2H, m), 1.78-2.08 (2H, m), 4.22 (1H, m), 5.60 (1H, ddt, J = 2.1,
108

2.7, 10.2 Hz), 5.70 (1H, ddt, J = 1.2, 3.9, 10.2 Hz), 7.34-7.45 (6H, m), 7.67-7.71 (4H, m); 13C
NMR (75 MHz in CDCl3) δ 19.21, 19.41, 25.04, 27.01, 32.18, 67.20, 127.50, 129.20, 129.49,
130.81, 134.62, 135.85, 135.87; HRMS (CI+) m/z calcd for C22H28OSi [M]+ 336.1909, found336.1904.

(E)-tert-Butyl[(1,7-diphenylhept-4-en-3-yl)oxy]diphenylsilane (189a)
OTBDPS
Ph

Ph
189a

182b(E)-1,7-diphenylhept-4-en-3-ol76) (1.32 g, 4.96 mmol)
189b (2.43 g, 4.81 mmol, 97%)

189b: colorless syrup; FT IR (neat) cm-1; 3068, 3025,

2999, 2930, 2893, 2856; 1H NMR (300 MHz in CDCl3) δ 1.06 (9H, s), 1.75 (2H, m), 2.18 (2H,q, J = 7.2 Hz), 2.49 (4H, m), 4.12 (1H, q, J = 6.3 Hz), 5.31 (1H, dt, J = 6.0 Hz, 15.6 Hz), 5.95
(1H, dd, J = 6.6 Hz, 15.6 Hz), 7.02 (1H, d, J = 6.6 Hz), 7.09-7.44 (16H, m), 7.64-7.70 (3H, m);
13

C NMR (75 MHz in CDCl3) δ 19.37, 27.07, 27.16, 31.12, 33.89, 35.48, 39.72, 74.06, 74.13,

125.53, 125.74, 127.29, 127.48, 128.26, 128.37, 129.38, 129.50, 130.61, 133.05, 134.44, 134.49,
135.93, 136.05, 141.84, 142.44; HRMS (CI+) m/z calcd for C35H41OSi [M+H]+; 505.2927, found505.2923.

(E)-tert-Butyldiphenyl[(1-phenylbut-2-en-1-yl)oxy]silane (189b)
OTBDPS

189b

51189b: colorless syrup; FT IR (neat) cm-1; 3070,
3050, 3030, 2998, 2960, 2932, 2889, 2857, 1589; 1H NMR (300 MHz in CDCl3) δ 1.67 (9H, s),
1.52 (3H, ddd, J = 0.9 Hz, 1.8 Hz, 6.6 Hz), 5.09 (1H, d, J = 6.9 Hz), 5.31 (1H, ddd, J = 0.9 Hz,
6.6 Hz, 15.3 Hz), 5.52 (1H, ddd, J = 1.8 Hz, 6.9 Hz, 15.3 Hz), 7.17-7.25 (7H, m), 7.32-7.45 (4H,m), 7.52 (2H, dt, J = 1.5 Hz, 6.0 Hz), 7.70 (2H, dt, J = 1.5 Hz, 6.0 Hz); 13C NMR (75 MHz in
CDCl3) δ 17.53, 17.59, 19.46, 26.99, 27.08, 76.77, 125.55, 126.09, 126.81, 127.35, 127.74,
109128.06, 129.44, 133.77, 134.47, 135.88, 136.02, 144.19; HRMS (CI+) m/z calcd for C26H31OSi[M+H]+; 387.2144, found 387.2146.

(E)-tert-Butyldiphenyl[(1-phenylhex-4-en-3-yl)oxy]silane (189c)
OTBDPS
Ph

189c



(E)-1-phenylhex-4-en-3-ol42) (725 mg, 4.11 mmol)

189c (1.65 g, 3.99 mmol, 97%)

189c: colorless syrup, FT IR (neat) cm-1; 3069, 3048,

 182b 

3025, 2996, 2961, 2931, 2890; 1H NMR (300 MHz in CDCl3) δ 1.06 (9H, s), 1.54 (3H, dd, J =1.5 Hz, 6.0 Hz), 1.77 (2H, m), 2.54 (2H, ddd, J = 3.0 Hz, 6.9 Hz, 9.9 Hz), 4.13 (1H, q, J = 6.3
Hz), 5.27 (1H, ddd, J = 6.0 Hz, 6.0 Hz, 15.3 Hz), 5.43 (1H, ddd, J = 1.5 Hz, 7.2 Hz, 15.3 Hz),7.05 (2H, dd, J = 1.5 Hz, 3.6 Hz), 7.14-7.25 (2H, m), 7.31-7.45 (6H, m), 7.66 (4H, m); 13C
NMR (75 MHz in CDCl3) δ14.19, 17.57, 19.37, 26.69, 27.12, 31.22, 31.62, 39.76, 74.16,
125.54, 126.30, 127.30, 127.48, 128.22, 128.31, 129.37, 129.50, 133.68, 134.42, 134.54, 135.90,
136.04, 142.38; HRMS (CI+) m/z calcd for C28H34OSi 415.2457 [M+H]+; found 415.2453.

tert-Butyldiphenyl{[(2R,E)-1-[(2S,4aS,8aR)-2,5,5,8a-tetramethyldecahydronaphthalen-1-yl]pent-3-en-2-yl]oxy}silane (189d)
OTBDPS

H189d

182b

(2R,E)-1-[(2S,4aS,8aR)-2,5,5,8a-tetramethyldecahy-dronaphthalen-1-yl]pent-3-en-2-ol25) (329 mg, 1.18 mmol)189d (580 mg, 1.12 mmol, 95%)
189d: colorless syrup; [α]22D = + 15.6 (c = 0.2, CHCl3), FT IR (neat) cm-1; 3069, 3047,
2993, 2931, 2855; 1H NMR (400 MHz in CDCl3) δ 0.65-0.76 (7H, m), 0.81 (3H, s), 1.03 (9H,s), 1.32 (1H, m), 1.18-1.52 (18H, m), 1.62 (1H, m), 3.96 (1H, dt, J = 4.8 Hz, 8.4 Hz), 5.11 (1H,
dd, J = 6.0 Hz, 15.6 Hz), 5.35 (1H, ddd, J = 1.6 Hz, 3.2 Hz, 15.6 Hz), 7.31-7.42 (6H, m),
110

7.62-7.68 (4H, m); 13C NMR (75 MHz in CDCl3) δ 15.75, 16.42, 17.32, 14.40, 18.40, 19.36,
21.54, 27.14, 30.38, 33.29, 33.46, 34.51, 35.39, 38.02, 39.11, 42.19, 48.34, 56.73, 73.87, 125.59,
127.08, 127.27, 129.16, 129.33, 134.63, 134.72, 135.04, 136.06, 136.19; HRMS (CI+) m/z calcd
for C35H51OSi [M-H]+; 515.3709, found 515.3715.

tert-Butyl{[(1S*,6S*)-6-isopropyl-3-methylcyclohex-2-en-1-yl]oxy}diphenylsilane (189e)
OTBDPSCH2OEt189e

182b

(1S*,5S*)-5-(ethoxymethyl)cyclohex-2-en-1-ol77) (520

mg, 3.33 mmol))189e (1.26 g, 3.20 mmol, 96%)

189e: colorless syrup; FT IR(neat) cm-1; 3070, 3050, 3030, 2998, 2960, 2932, 2889, 2857, 1589; 1H NMR (300 MHz in
CDCl3) δ 1.07 (9H, s), 1.16 (3H, t, J = 7.2 Hz), 1.36 (3H, dt, J = 2.7 Hz, 12.0 Hz), 1.67-1.88(2H, m), 1.90-2.04 (2H, m), 3.28 (2H, m), 3.41 (2H, q, J = 7.2 Hz), 4.34 (1H, m), 5.57-5.68 (2H,m), 7.35-7.46 (6H, m), 7.70 (4H, m); 13C NMR (100 MHz in CDCl3) δ 15.16, 19.14, 26.98,
28.62, 33.32, 35.75, 66.22, 98.86, 75.33, 127.18, 127.51, 129.52, 131.86, 134.37, 135.83;
HRMS (CI+) m/z calcd for C25H33O2Si [M-H]+; 393.2250, found 393.2245.

tert-Butyl{[(1S*,6S*)-6-isopropyl-3-methylcyclohex-2-en-1-yl]oxy}diphenylsilane (189f)
OTBDPS

189f

182b

(1S*,6S*)-6-isopropyl-3-methylcyclohex-2-en-1-ol78)(680 mg, 4.41 mmol)189f (1.66 g, 4.23 mmol, 96%)

189f: colorless syrup; FT IR(neat) cm-1; 3070, 3050, 3030, 2998, 2960, 2932, 2889, 2857, 1589; 1H NMR (400 MHz in
CDCl3) δ 0.52 (3H, d, J = 6.8 Hz), 0.75 (3H, d, J = 6.8 Hz), 1.05 (9H, s), 1.26 (1H, m), 1.41
(1H, m), 1.54 (3H, s), 1.70-1.89 (3H, m), 4.07 (1H, dd, J = 1.6 Hz, 3.6 Hz), 5.26 (1H, d, J = 1.6
111Hz), 7.34-7.41 (6H, m), 7.70-7.72 (4H, m); 13C NMR (100 MHz in CDCl3) δ 17.40, 19.40,
20.03, 21.26, 23.26, 25.55, 27.14, 29.33, 47.32, 70.36, 125.02, 127.30, 127.47, 129.30, 129.43,
134.42, 135.00, 136.00;

HRMS (CI+) m/z calcd for C26H36OSi [M]+; 392.2535, found392.2530.

2-{(1S*,5R*)-5-[(tert-Butyldiphenylsilyl)oxy]-4-methylcyclohex-3-en-1-yl}propan-2-yl
acetate (189g)
OTBDPSOAc

189g

 182b 2-[(1S*,5R*)-5-hydroxy-4-methylcyclohex-3-en-1-yl]propan-2-yl acetate 79) (680 mg, 4.41 mmol) 189g (1.66 g, 4.23 mmol, 96%)

189g: colorless syrup; FT IR (neat) cm-1; 3070, 3050, 3030, 2998, 2960, 2932, 2889, 2857,
1589; 1H NMR (500 MHz in CDCl3) δ 1.07 (9H, s), 1.21 (1H, dt, J = 3.5 Hz, 13.0 Hz), 1.37
(3H, s), 1.43 (3H, s), 1.52 (3H, s), 1.76 (1H, m), 1.85 (1H, dd, J = 1.5 Hz, 6.0 Hz, 13.0 Hz),1.92 (3H, s), 2.91 (1H, m), 2.36 (1H, m), 4.04 (1H, s), 5.47 (1H, dd, J = 1.5 Hz, 3.5 Hz),7.35-7.44 (6H, m), 7.70 (4H, m); 13C NMR (125 MHz in CDCl3) δ 19.52, 21.52, 22.48, 23.11,
23.20, 26.64, 27.10, 32.76, 37.53, 69.89, 124.41, 127.41, 127.51, 129.48, 129.61, 134.41,
134.71, 136.07, 136.17, 170.47; HRMS (CI+) m/z calcd for C28H37O3Si [M-H]+; 449.2512, found449.2520.

(E)-2,2,11,11-Tetramethyl-3,3,5,8,10,10-hexaphenyl-4,9-dioxa-3,10-disiladodec-6-ene(189h)OTBDPSOTBDPS

189h

 182b (E)-1,4-diphenylbut-2-ene-1,4-diol 79) (783 mg, 3.26112mmol){TBDPSCl (1.5 mL, 7.82 mmol){imidazole (1.33 g, 19.6 mmol) 189h (2.24 g,
mmol, 94%)L|189h: white powder; FT IR (neat) cm-1; 3069, 3048, 3028, 2957, 2930,

2856; 1H NMR (300 MHz in CDCl3) δ 0.97-1.51 (18H, s), 4.98 (2H, m), 5.46 (1H, dd, J = 1.8
Hz, 4.8 Hz), 6.52 (2H, dt, J = 1.5 Hz, 6.0 Hz), 6.57 (1H, dd, J = 1.8 Hz, 4.8 Hz), 7.17-7.23 (2H,m), 7.32-7.45 (4H, m), 7.70 (2H, dt, J = 1.2 Hz, 3.0 Hz); 13C NMR (75 MHz in CDCl3) δ 19.38,
26.94, 76.25, 75.67, 126.17, 126.37, 126.85, 127.24, 127.28, 127.34, 129.40, 129.43, 132.29,
132.90, 133.28, 133.83, 133.96, 135.85, 135.89, 143.39; HRMS (CI+) m/z calcd for C48H51O2Si2[M-H]+; 715.3428, found 715.3416.

01-'ABMhOf

0.1 M 1(+/%1\xrF(C2B10H11HgCl/AgOTf)sq
64 (56.9 mg, 0.150 mmol)0.1 M d\CH2Cl2 (1.5 mL)a]{AgOTf (38.5 mg, 0.150mmol)H`

@

8i

|sq

~U9G

|

K{ `I
rF{1

30>ySR3zE[5{<pJ|TRKa]PC
u;

gN

}

tert-Butyl (E)-2-tosyl-2-(undec-6-en-5-yl)hydrazine-1-carboxylate (183)

Boc

H
N

NTs

n-C4H9n-C4H9183

182b (1.08 g, 2.64 mmol)  tert-butyl 2-tosylhydrazine-1-carboxylate52) (69) (755 mg, 3.96mmol)  CH2Cl2 (8.7 mL)a]{7?sqmL) 0 °C@{0 °C

10 >ySR

0.1 M 1(+/%1\xrF(1.32|X{oj\^@BM:Y{|VWkd\lw,&".

6e{ctKVWf CH2Cl2

3 DQ=

bn

Z_/.2,$/)4(*!3/vw#1 20:1 

4:1)

|L

mq

180 (902 mg, 2.06 mmol, 78%) 64 (48.2 mg, 0.127 mmol, 96%)L|

180: colorless syrup; FT IR (neat) cm-1; 3313, 3238, 3138, 2957, 2929, 2857, 2856; 1H NMR
113

(500 MHz in DMSO, 70 °C) δ 0.85 (6H, m), 1.25 (20H, m), 1.93 (3H, m), 2.43 (3H, s), 4.18
(1H, br d, J = 6.0 Hz), 5.27 (1H, m), 5.47 (1H, m), 7.36 (2H, d, J = 7.5 Hz), 7.79 (2H, d, J = 7.5
Hz), 8.59 (NH, br s); 13C NMR (125 MHz in DMSO, 70 °C) δ 14.06, 21.36, 21.96, 22.18, 27.92,
28.13, 28.25, 28.47, 30.92, 31.68, 32.38, 62.06, 80.09, 128.22, 128.60, 129.55, 129.67, 143.80,
155.48; HRMS(CI+) m/z calcd for C23H39N2O4S [M-H]+; 437.2474, found 437.2479.

Homodimer (184)n-C4H9n-C4H9(E/Z = 2:1)

O

n-C4H9n-C4H9184

184: colorless syrup; FT IR (neat) cm-1; 2957, 2929, 2859; 1H NMR (400 MHz in CDCl3)
δ 0.85-0.92 (12H, m), 1.13-1.59 (24H, m), 2.03 (4H, m), 3.68 (2H, m), 5.19 (major 1H, ddt, J =1.2 Hz, 8.0 Hz, 15.2 Hz), 5.32 (minor 1H, ddt, J = 1.6 Hz, 7.6 Hz, 15.6 Hz), 5.48 (4H, m); 13C
NMR (125 MHz in CDCl3) δ (major peak) 13.93, 14.10, 22.17, 22.64, 27.80, 31.56, 31.97,
35.78, 76.67, 131.60, 133.23; (minor peak) 13.95, 14.11, 22.22, 22.76, 27.64, 31.47, 31.97,
35.08, 78.30, 132.08, 132.11; HRMS (CI+) m/z calcd for C22H42O [M]+; 322.3236 found322.3238.

tert-Butyl 2-(cyclohex-2-en-1-yl)-2-tosylhydrazine-1-carboxylate (190)

N
Ts

NHBoc

190

 (180&$.

"/186 (113 mg, 0.337 mmol)

69 (145 mg, 0.506 mmol)

190 (91.1 mg, 0.249 mmol, 74%)#/64 (6.28 mg, 0.0166 mol, 98%)

0

190: colorless syrup; FT IR (neat) cm-1; 3313, 3238, 3138, 2957, 2929, 2857, 2856; MS (Cl)m/z 367 [M+H]+; HRMS (CI+) C18H27N2O4S m/z calcd for 367.1692, found 367.1710. 190
13

C-NMR



+%!-

0
114

/'

1

H,

*Boc),tert-Butyl (E)-2-(1,7-diphenylhept-4-en-3-yl)-2-tosylhydrazine-1-carboxylate (191a)
BocHN

NTs

Ph

Ph
191a

 (180&$.

"/189a (173 mg, 0.343 mmol)

69 (147 mg, 0.515mmol)191a (91.1 mg, 0.249 mmol, 74%)#/64 (6.40 mg, 0.0169 mol, 98%)

0191a: colorless syrup; FT IR (neat) cm-1; 3313, 3238, 3138, 2957, 2929, 2857, 2856; MS(Cl) m/z 437 [M-H]+; HRMS (CI+) C23H39N2O4S m/z calcd for 437.2474, found 437.2479. 191a1

H, 13C-NMR



+%!-

/'*Boc

),

tert-Butyl (E)-2-(4-phenylbut-3-en-2-yl)-2-tosylhydrazine-1-carboxylate (191b)
BocHN

NTs

191b

 (180&$.

"/189b (130 mg, 0.355 mmol)

69 (144 mg, 0.504mmol)191b (89.9 mg, 0.271 mmol, 81%)#/64 (5.98 mg, 0.0160 mol, 95%)

0191b: white powder; FT IR (neat) cm-1; 3313, 3238, 3138, 2957, 2929, 2857, 2856; MS(Cl) m/z 417 [M+H]+; HRMS (CI+) C22H29N2O4S m/z calcd for 417.1848, found 417.1825. 191b
1

H, 13C-NMR



+%!-

/'*Boc

),0191b (50 mg) was crystallized from Hexane/AcOEt (4 mL, 5:1) at room temperature.
CCDC 1556661 contains the supplementary crystallographicdata for this paper. The data can beobtained free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/getstructures.

115

tert-Butyl(E)-2-(6-phenylhex-3-en-2-yl)-2-tosylhydrazine-1-carboxylate (191c1) tert-Butyl(E)-2-(1-phenylhex-4-en-3-yl)-2-tosylhydrazine-1-carboxylate (191c2)
BocHN

NHBoc

TsN

NTs
Ph

Ph

191c2

191c1

 

*180

!(

&0

$1189c (130 mg, 0.355 mmol)

191c1 (85.4 mg, 0.192 mmol, 57%)

69 (144 mg, 0.504 mmol)

191c2 (27.0 mg, 0.061 mmol, 18%)%164 (6.14

mg, 0.0162 mol, 96%)"2191c1: colorless syrup; FT IR (neat) cm-1; 3234, 3132, 3027,
2976, 2927, 2859; MS (Cl) m/z 445 [M+H]+; HRMS (CI+) C24H33N2O4S m/z calcd for 445.2161,
found 445.2174. 191c2: colorless syrup; FT IR (neat) cm-1; 3234, 3133, 3027, 2974, 2927, 2859;
MS (Cl) m/z 444 [M]+; HRMS (CI+) C24H31N2O4S m/z calcd for 444.2083, found 444.2056.
191c1191c3),Boc

1

H, 13C-NMR

-'#/

1+.2

tert-Butyl-2-{(E)-5-[(2S,4aS,8aR)-2,5,5,8a-tetramethyldecahydronaphthalen-1-yl]pent-3-en-2-yl}-2-tosylhydrazine-1-carboxylate (191d1)
tert-Butyl-2-{(E)-1-[(2S,4aS,8aR)-2,5,5,8a-tetramethyldecahydronaphthalen-1-yl]pent-3-en-2-yl}-2-tosylhydrazine-1-carboxylate (191d2)

116

BocHN

H



TsN

NTs

H

191d1

"/180

#+

NHBoc

191d2

'6189d (130 mg, 0.355 mmol))5mmol)191d1 (110 mg, 0.202 mmol, 62%)69 (140 mg, 0.488

191d2 (32.0 mg, 0.059 mmol, 18%)(664(5.98 mg, 0.0160 mol, 98%)$!7191d1: colorless syrup; [α]23D = + 13.0 (c = 1.4,
CHCl3), FT IR (neat) cm-1; 3377, 3313, 3325, 3138, 2931, 2849; MS (Cl) m/z 545 [M-H]+;
HRMS (CI+) C31H49N2O4S m/z calcd for 545.3413, found 545.3421. 191d2: colorless syrup;[α]24D = + 15.6 (c = 0.4, CHCl3); FT IR (neat) cm-1; 3313, 3238, 3138, 2957, 2929, 2857, 2856;
MS (Cl) m/z 545 [M-H]+; HRMS (CI+) C31H49O2O4S m/z calcd for 545.3413, found 545.3411.
191d1191d8
,

1Boc



1

H, 13C-NMR

2*%46037

tert-Butyl 2-(5-(ethoxymethyl)cyclohex-2-en-1-yl)-2-tosylhydrazine-1-carboxylate (191e)
TsN

NHBoc
(syn/anti = 1:3)

CH2OEt

191e



"/180

#+

)5

'6189e (123 mg, 0.311 mmol)

69 (134 mg, 0.467 mmol)

191e (104 mg, 0.246 mmol, 79%)(664 (5.69 mg, 0.0150 mmol, 96%)$!7
191e: colorless syrup; FT IR (neat) cm-1; 3308, 3240, 3139, 3028, 2975, 2925, 2855; MS (Cl)m/z 423 [M-H]+; HRMS (CI+) C21H31N2O5S m/z calcd for 423.1954, found 423.1963. 191e
C-NMR

2*%4

.

.&7

13

6Syn/anti-1Boc

6,

1Boc

tart-Butyl 2-[(1S*,6S*)-6-isopropyl-3-methylcyclohex-2-en-1-yl]-2-tosylhydrazine-1carboxylate (191f)
117

1

H,

03

TsN

NHBoc

191f

 !.180"*(4&5189f (125 mg, 0.318 mmol)

69 (137 mg, 0.477 mmol)

191f (104 mg, 0.245 mmol, 77%)'564 (5.92 mg, 0.0156 mol, 98%)#6

191f: colorless syrup; FT IR (neat) cm-1; 3387, 3308, 3234, 3138, 2956, 2930, 2871; MS (Cl+)
m/z 421 [M-H]+; HRMS (CI+) C22H33N2O4S m/z calcd for 421.2187, found 421.2174. 191f
13

C-NMR61)$35Syn/anti,0Boc5+0Boc

1

H,

/2

-%6

tert-Butyl 2-[(1R*,5S*)-5-(2-acetoxypropan-2-yl)-2-methylcyclohex-2-en-1-yl]-2-tos
ylhydrazine-1-carboxylate (191g)
TsN

NHBoc

OAc
191g

 !.180"*(4&5189g (147 mg, 0.326 mmol)

69 (140 mg, 0.489mmol)191g (128 mg, 0.267 mmol, 82%)'564 (5.99 mg, 0.0158 mmol, 97%)#6191g: colorless syrup; FT IR (neat) cm-1; 3313, 3238, 3138, 2957, 2929, 2857, 2856; MS(Cl) m/z 481 [M+H]+; HRMS (CI+) C24H36N2O6S m/z calcd for 481.2372, found 481.2365. 191g
1

H, 13C-NMR1)$3/2.

(1E,3E)-1,4-Diphenylbuta-1,3-diene (109h)

192h

118

5+0Boc

!$@180%4.P*

Q189h (246 mg, 0.343 mmol)69 (147 mg, 0.515 mmol)

192h (43.9 mg, 0.213 mmol, 62%)+Q64 (6.26 mg, 0.0165 mol, 96%)&#

R

192h: white powder; FT IR (neat) cm-1; 3077, 3055, 3016, 2946; 1H NMR (500 MHz in CDCl3)
δ 6.67 (2H, dd, J = 3.0 Hz, 12.8 Hz), 6.96 (2H, dd, J = 3.0 Hz, 12.8 Hz), 7.22-7.26 (2H, m),
7.32-7.35 (4H, m), 7.44-7.46 (4H, m); 13C NMR (125 MHz in CDCl3) δ 126.38, 127.56, 128.66,
129.23, 132.81, 137.33 ; HRMS (CI+) m/z calcd for C16H14 [M]+; 206.1006 found 206.1104.

'!7FB

HBoc!",A-@(186, 190’, 191a-h’JK)(E)-4-Methyl-N-(undec-6-en-5-yl)benzenesulfonohydrazide (186)
H

H
N

N

n-C4H9Ts
n-C4H9186

183 (156 mg, 0.310 mmol), '!7FMN;8(1.0 M, 6.2 mmol, 6 mL) 0 °C

Et2O
+



Q(:

/

5 2O10. IC79

R35D>7EN

",6Q35@

?Q=L)<G

R186: yellow syrup; FT IR (neat) cm-1: 3368, 3029, 2956, 2928, 2870, 2858. 1H NMR (300

MHz in CDCl3): δ 0.87 (6H, m), 1.13-1.33 (8H, m), 1.52-1.67 (2H, m), 1.86 (2H, q, J = 6.6 Hz),2.42 (3H, s), 3.40 (NH2, s), 4.39, (1H, q, J = 7.5 Hz), 5.18 (1H, ddd, J = 1.5 Hz, 7.5 Hz, 15.6
Hz), 5.50 (1H, dt, J = 6.6 Hz, 15.6 Hz), 7.29 (2H, d, J = 7.8 Hz), 7.73 (2H, d, J = 7.8 Hz); 13C
NMR (75 MHz in CDCl3): δ 13.86, 14.00, 21.48, 22.11, 22.28, 28.28, 31.05, 31.65, 31.95,
60.35, 125.44, 128.25, 128.37, 134.54, 134.94, 143.51; HRMS (CI+) m/z calcd for C18H31N2O2S[M+H]+; 339.3006, found 339.2907.

N-(Cyclohex-2-en-1-yl)-4-methylbenzenesulfonohydrazide (190’)

N
Ts

NH2

190’

119

186190 (91.1 mg, 0.249 mmol)





(4.98 mL, 4.98 mL)190’ (66.6 mg, 0.249 mmol, quant.) 190a’: yellow syrup;
FT IR (neat) cm-1; 3366, 3026, 3061, 2934, 2863; 1H NMR (300 MHz in C6D6) δ 1.32-1.78 (6H,m), 1.93 (3H, s), 3.19 (NH2, s), 4.96 (1H, m), 5.23 (1H, dt, J = 1.2 Hz, 10.2 Hz), 5.61 (1H, m),
6.83 (2H, dd, J = 3.9 Hz, 7.8 Hz), 7.85 (2H, dd, J = 3.9 Hz, 7.8 Hz); 13C NMR (100 MHz in
C6D6) δ 21.18, 21.43, 24.55, 26.82, 56.0, 126.3, 128.32, 129.72, 133.28, 136.00, 143.42; HRMS(CI+) m/z calcd for C13H19N2O2S [M+H]+; 267.1167 found 267.1150.

(E)-N-(1,7-Diphenylhept-4-en-3-yl)-4-methylbenzenesulfonohydrazide (191a’)
H 2N

NTs

Ph

Ph
191a’

186191a (154 mg, 0.288 mmol)





(5.76 mL, 5.76 mmol)191a’ (97.7 mg, 0.288 mmol, quant.) 191a’: yellow
syrup; FT IR (neat) cm-1; 3368, 3029, 2956, 2928, 2870, 2858; 1H NMR (300 MHz in CDCl3)
δ 0.87 (6H, m), 1.13-1.33 (8H, m), 1.52-1.67 (2H, m), 1.86 (2H, q, J = 6.6 Hz), 2.42 (3H, s),3.40 (NH2, s), 4.39, (1H, q, J = 7.5 Hz), 5.18 (1H, ddd, J = 1.5 Hz, 7.5 Hz, 15.6 Hz), 5.50 (1H,
dt, J = 6.6 Hz, 15.6 Hz), 7.29 (12H, d, J = 7.8 Hz), 7.73 (2H, d, J = 7.8 Hz); 13C NMR (75 MHz
in CDCl3) δ 13.86, 14.00, 21.48, 22.11, 22.28, 28.28, 31.05, 31.65, 31.95, 60.35, 125.44,
128.25, 128.37, 134.54, 134.94, 143.51; HRMS (ESI+) m/z calcd for C18H31N2O2S [M+H]+;
339.3006 found 339.2907.

(E)-4-Methyl-N-(4-phenylbut-3-en-2-yl)benzenesulfonohydrazide (191b’)
H 2N

NTs

191b’

186191b (88.9 mg, 0.271 mmol)



(5.42 mL, 5.42 mmol)191b’ (85.9 mg, 0.271 mmol, quant.) 191b’: yellow
120

syrup; FT IR (neat) cm-1; 3367, 3084, 3061, 3025, 2978, 2928, 2857; 1H NMR (400 MHz in
C6D6) δ 1.79 (3H, d, J = 6.9 Hz), 2.74 (NH2, s), 5.00 (1H, m), 5.25 (1H, ddt, J = 0.9 Hz, 8.1 Hz,
16.2 Hz), 6.23 (1H, d, J = 16.2 Hz), 6.75 (1H, d, J = 8.1 Hz), 7.03-7.16 (2H, m), 7.17 (2H, dt, J= 1.2 Hz, 7.6 Hz), 7.26 (1H, m), 7.30 (2H, d, J = 8.0 Hz), 7.74 (2H, d, J = 8.0 Hz), 7.65 (2H, d,
J = 8.0 Hz); 13C NMR (100 MHz in C6D6) δ 17.7, 21.1, 34.02, 56.3, 132.3, 135.3, 135.9, 126.8,
127.7, 128.0, 127.9, 128.3, 128.7, 143; HRMS (CI+) m/z calcd for C17H21N2O2S [M+H]+;
317.1324 found 317.1337.

(E)-4-Methyl-N-(6-phenylhex-3-en-2-yl)benzenesulfonohydrazide (191c1’)
H 2N

NTs

Ph

191c1’

186191c1 (85.4 mg, 0.192 mmol)



(3.84 mL, 3.84 mmol)191c1’ (66.3 mg, 0.192 mmol, quant.) 191c1’: yellow
syrup; FT IR (neat) cm-1; 3364, 3064, 3027, 2929, 2855; 1H NMR (400 MHz in CDCl3) δ 1.48
(3H, dd, J = 1.2 Hz, 6.8 Hz), 1.65 (1H, m), 1.96 (1H, m), 2.36 (3H, s), 2.57 (2H, m), 3.40 (NH2,br s), 4.37 (1H, q, J = 6.8 Hz), 5.15 (1H, ddd, J = 1.2 Hz, 7.6 Hz, 15.2 Hz), 5.51 (1H, m),
7.09-7.13 (3H, m), 7.19-7.24 (4H, m), 7.65 (2H, d, J = 8.0 Hz); 13C NMR (100 MHz in CDCl3)
δ 13.10, 16.79, 27.24, 29.06, 55.54, 121.07, 122.24, 123.58, 123.67, 123.69, 124.70, 125.28,
129.94, 137.04, 139.04; HRMS (CI+) m/z calcd for C19H25N2O2S [M+H]+; 345.1637
found 345.1634.

(E)-4-Methyl-N-(1-phenylhex-4-en-3-yl)benzenesulfonohydrazide (191c2’)
TsN

NH2

Ph

191c2’

186191c2 (87.2 mg, 0.197 mmol)



(3.94 mL, 3.94 mmol)191c2’ (68.1 mg, 0.197 mmol, quant.) 191c2’: yellow
121syrup; FT IR (neat) cm-1; 3367, 3084, 3061, 3025, 2978, 2928, 2857; 1H NMR (400 MHz in
CDCl3) δ 1.17 (3H, d, J = 6.8 Hz), 2.25 (2H, m), 2.42 (3H, s), 2.59 (2H, d, J = 8.0 Hz), 3.30
(NH2, s), 4.67 (1H, quin., J = 6.8 Hz), 5.25 (1H, ddt, J = 1.6 Hz, 6.0 Hz, 15.6 Hz), 5.51 (1H, ddt,
J = 1.6 Hz, 6.8 Hz, 15.6 Hz), 7.14 (2H, dd, J = 1.2 Hz, 8.4 Hz), 7.17 (2H, dt, J = 1.2 Hz, 7.6
Hz), 7.26 (1H, m), 7.30 (2H, d, J = 8.0 Hz), 7.74 (2H, d, J = 8.0 Hz); 13C NMR (100 MHz in
CDCl3) δ 17.20, 21.57, 34.02, 35.31, 55.40, 125.90, 128.27, 128.31, 128.39, 128.48, 129.55,
132.94, 134.64, 141.48, 143.76; HRMS (CI+) m/z calcd for C19H25N2O2S [M+H]+; 345.1637
found 345.1612.

4-Methyl-N-{(E)-5-[(2S,4aS,8aR)-2,5,5,8a-tetramethyldecahydronaphthalen-1-yl]pent-3-en-2-yl}benzenesulfonohydrazide (191d1’)
H 2N

H

NTs

191d1’

186191d1(110 mg, 0.202 mmol)





(4.04 mL, 4.04 mmol)191d1’ (90.1 mg, 0.202 mmol, quant.) 191d1’: yellow
syrup; [α]23D = + 9.6 (c = 0.3, CHCl3); FT IR (neat) cm-1; 3368, 2927, 2856, 2850; 1H NMR(500 MHz in CDCl3) δ 0.78-0.83 (4H, m), 0.85 (3H, s), 1.04-1.11 (2H, m), 1.20 (3H, d, J = 5.2
Hz), 1.26-1.72 (16H, m), 1.81 (1H, m), 2.08 (1H, t, d, J = 5.5 Hz), 2.43 (3H, s), 3.57 (NH2, br s),
4.68 (1H, quin., J = 5.2 Hz), 5.27 (1H, dt, J = 6.0 Hz, 15.5 Hz), 5.46 (1H, m) 7.31 (2H, d, J =8.0 Hz), 7.76 (2H, d, J = 8.0 Hz); 13C NMR (125 MHz, in CDCl3) δ 15.10, 15.25, 16.33, 17.38,
17.45, 17.57, 18.46, 21.57, 21.58, 21.62, 29.26, 29.30, 29.70, 29.84, 29.86, 33.32, 33.53, 34.78,
34.82, 38.20, 38.24, 39.61, 39.63, 42.10, 53.41, 53.65, 55.37, 55.56, 56.73, 127.45, 128.03,
128.21, 128.31, 18.35, 129.24, 129.54, 129.57, 134.39, 134.68, 134.86, 134.93, 143.70; HRMS(CI+) m/z calcd for C26H42N2O2S [M]+; 446.2967, found 446.2970.

122

4-Methyl-N-{(E)-1-[(2S,4aS,8aR)-2,5,5,8a-tetramethyldecahydronaphthalen-1-yl]pent-3-en-2-yl}benzenesulfonohydrazide (191d2’)
TsN

H

NH2

191d2’

186191d2 (105 mg, 0.193 mmol)
(4.04 mL, 4.04 mmol)191d2’ (88.7 mg, 0.193 mmol, quant.)191d2’: yellow

syrup; [α]21D = + 21.2 (c = 0.4, CHCl3); FT IR (neat) cm-1; 3368, 3258, 2925, 2957, 2857, 2852;
1

H NMR (400 MHz in CDCl3) δ 0.80-0.96 (12H, m), 1.10-1.78 (18H, m), 2.43 (3H, s), 4.38

(1H, q, J = 3.2 Hz, 8.4 Hz), 4.97 (minor product peak, 1H, dt, J = 7.6 Hz, 15.2 Hz), 5.20 (1H,
ddd, J = 3.2 Hz, 7.6 Hz, 15.2 Hz), 5.32 (minor product peak, 1H, dd, J = 6.0 Hz, 15.2 Hz), 5.55
(1H, m), 5.2-5.65 (2H, m), 7.33 (2H, m), 7.75 (2H, m); HRMS (CI+) m/z calcd for C26H43N2O2S[M+H]+; 447.3045, found 447.3038.

N-[5-(Ethoxymethyl)cyclohex-2-en-1-yl]-4-methylbenzenesulfonohydrazide (191e’)
TsN

NH2(syn/anti = 1:3)

CH2OEt191e’186191e (104 mg, 0.246 mmol)





(4.92 mL, 4.92 mmol)191e’ (78.0 mg, 0.246 mmol, quant.) 191e’: yellow syrup;
FT IR (neat) cm-1; 3366, 3267, 3205, 2973, 2929, 2863, 2800; 1H NMR (300 MHz in CDCl3)
δ 1.16-1-24 (3H, m), 1.57-2.27 (4H, m), 2.44 (3H, s), 3.27-3.31 (2H, m), 3.45 (2H, m), 4.66
(1H, m), 4.79 (syn 1H, m), 5.15 (syn 1H, m), 5.25 (1H, m), 5.97 (1H, m), 7.30 (2H, d, J = 8.0Hz), 7.74 (2H, d, J = 8.0 Hz); HRMS (CI+) m/z calcd for C17H21N2O2S [M+H]+; 317.1324
found 317.1337.

123

N-[(1S*,6S*)-6-Isopropyl-3-methylcyclohex-2-en-1-yl]-4-methylbenzenesulfonohydrazide(191f’)
TsN

NH2

191f’

186191f (104 mg, 0.245 mmol)





(4.90 mL, 4.90 mmol)191f’ (79.2 mg, 0.245 mmol, quant.) 191f’; yellow syrup;
FT IR (neat) cm-1; 3359, 2956, 2926, 2870, 1723; 1H NMR (500 MHz in CDCl3) δ 0.86 (3H, d,
J = 7.0 Hz), 0.94 (3H, d, J = 7.0 Hz), 1.26-1.38 (5H, m), 1.51 (1H, dt, J = 2.5 Hz, 10.0 Hz),1.70-1.74 (1H, m), 1.89-2.07 (3H, m), 2.48 (3H, s), 3.41 (NH2, br s), 4.54 (1H, m), 4.72 (1H, s),7.33 (2H, d, J = 8.0 Hz), 7.79 (2H, d, J = 8.0 Hz); 13C NMR (125 MHz in CDCl3) δ 15.96,
21.15, 21.24, 21.59, 23.45, 26.34, 30.39, 41.30, 59.25, 119.47, 128.24, 129.61, 135.36, 143.42,
143.67; HRMS (CI+) m/z calcd for C17H27N2O2S [M+H]+; 323.1793, found 323.1798.

2-[(1S*,5R*)-4-Methyl-5-(1-tosylhydrazineyl)cyclohex-3-en-1-yl]propan-2-yl

acetate(191g’)
TsN

NH2

OAc
191g’

186191g (128 mg, 0.267 mmol)





(5.34 mL, 5.34 mmol)191g’ (102 mg, 0.267 mmol, quant.) 191g’: yellow syrup;
FT IR (neat) cm-1; 3313, 3238, 3138, 2957, 2929, 2857, 2856; 1H NMR (500 MHz in CDCl3)
δ 1.24 (3H, s), 1.39 (3H, s), 1.61 (3H, s), 1.72-1.81 (3H, m), 1.86 (3H, s), 2.07 (1H, m), 2.43
(3H, s), 2.73 (1H, dt, J = 3.0 Hz, 14.5 Hz), 3.54 (NH2, s), 4.55 (1H, d, J = 5.5 Hz), 5.79 (1H, J =4.0 Hz), 7.33 (2H, d, J = 8.0 Hz), 7.79 (2H, d, J = 8.0 Hz); 13C NMR (125 MHz in CDCl3) δ
20.88, 21.55, 22.34, 22.60, 23.99, 26.64, 29.71, 29.77, 37.38, 56.41, 84.54, 128.00, 128.05,

124129.68, 130.56, 135.24, 143.74; HRMS (CI+) m/z calcd for C19H28N2O4S [M]+; 380.1770, found380.1771.

MIK./7G9F(E)-Undec-5-ene (188)n-C4H9n-C4H9188

188 (156 mg, 0.310 mmol)QR&DA(6 mL) U+8%&(3 g)3C
U3C-

W>S=<. /74%&!(/QR&(100:1);,)P4UELV6@B$#'"$& 20:1  4:1)

JO

*(!(/QR

188 (39.2 mg, 0.254 mmol, 82%)6V188: colorless

syrup; FT IR (neat) cm-1; 2957, 2931, 2871; 1H NMR (400 MHz in CDCl3) δ 0.88 (6H, m), 1.27
(10H, m), 1.97 (4H, m), 5.39 (2H, m); 13C NMR (100 MHz in CDCl3) δ 14.31, 14.43, 22.54,
22.90, 29.689, 31.75, 32.18, 32.64, 32.93, 130.64, 130.71; HRMS (CI+) m/z calcd for C11H22[M]+; 154.1722 found 154.1720.

Cyclohexene (120a)120.0F 188

1?:T

P4U*&'*&5

U190’ (1.35 g, 5.04 mmol)UD2 Et2O(2 mL)

NH



120 (357 mg, 4.33 mmol, 86%)6V120:

colorless liquid; FT IR (neat) cm-1; 3154, 3092, 2927, 2854, 2837; 1H NMR (300 MHz in
CDCl3) δ 1.60 (4H, m), 1.99 (4H, m), 5.67 (2H, t, J = 1.5 Hz); 13C NMR (75 MHz in CDCl3)
δ 22.61, 25.13, 127.21; HRMS (CI+) m/z calcd for C6H10 [M]+; 82.0783, found 82.0783.

(E)-Hept-3-ene-1,7-diyldibenzene (192a)
125

Ph

Ph
192a

188
mmol, 75%)191a’ (145 mg, 0.333 mmol)192a (62.5 mg, 0.250

192a: colorless syrup; FT IR (neat) cm-1; 2953, 2922, 2852; 1H NMR (300

MHz in CDCl3) δ 1.66 (2H, quin., J = 7.2 Hz), 2.02 (2H, m), 2.32 (2H, m), 2.57 (1H, t, J = 7.2
Hz), 2.67 (1H, t, J = 7.2 Hz), 5.45 (2H, m), 7.14-7.18 (5H, m), 7.23-7.24 (4H, m); 13C NMR(100 MHz, in CDCl3) δ 31.22, 32.03, 34.45, 35.29, 36.12, 125.62, 125.72, 128.24, 128.48,
129.91, 130.61, 142.13, 142.63; HRMS (CI+) m/z calcd for C19H22 [M]+; 250.1722, found250.1748.

(E)-But-2-en-1-ylbenzene (192b)

192b

188
mmol, 43%)191b’ (102 mg, 0.321 mmol)192b (18.2 mg, 0.138

192b: colorless syrup; FT IR (neat) cm-1; 3050, 3019, 2976; 1H NMR (300

MHz in CDCl3) δ 1.69 (3H, m), 3.21 (2H, d, J = 5.7 Hz), 5.55 (2H, m), 7.16-7.25 (2H, m),
7.28-7.31 (3H, m); 13C NMR (75 MHz in CDCl3) δ 17.91, 39.06, 125.88, 126.37, 128.35,
128.88, 130.05, 141.08; HRMS (CI+) m/z calcd for C10H11 [M-H]+; 131.0861 found 131.0863.

(E)-Hex-4-en-1-ylbenzene (192c1)
Ph

192c1

188



191c1’ (117 mg, 0.340 mmol)192c1 (40.8 mg, 0.255

mmol, 75%) 192c1: colorless syrup; FT IR (neat) cm-1; 3085, 3062, 3025, 2960, 2931,
2855; 1H NMR (500 MHz in CDCl3) δ 1.65-1.70 (5H, m), 2.02 (2H, m), 2.60 (2H, t), 2.67 (2H,m), 5.63 (2H, m), 7.17 (3H, m), 7.28 (2H, m); 13C NMR (100 MHz in CDCl3) δ 17.96, 31.29,

12632.14, 35.38, 125.19, 125.60, 128.24, 128.46, 131.07, 142.67 ; HRMS (CI+) m/z calcd for
C12H16 [M]+; 160.1252 found 160.1245.

(E)-Hex-3-en-1-ylbenzene and (Z)-Hex-3-en-1-ylbenzene (192c2)(E/Z = 15:1)

Ph

192c2

188
mmol, 72%)191c2’ (108 mg, 0.313 mmol)192c2 (36.1 mg, 0.225

192c2: colorless syrup; FT IR (neat) cm-1; 3023, 2968, 2923, 2854; 1H

NMR (400 MHz in CDCl3) (E-isomer) δ 0.96 (3H, t, J = 7.6 Hz), 2.00 (2H, m), 2.30 (2H, m),
2.67 (2H, m), 5.63 (2H, m), 7.17 (3H, m), 7.28 (2H, m); 13C NMR (100 MHz in CDCl3)(E-isomer) δ 13.88, 25.56, 34.44, 36.14, 125.65, 128.19, 128.31, 128.44, 132.63, 142.20;
HRMS (CI+) m/z calcd for C12H16 [M]+; 160.1252 found 160.1245.

(4aR,6S,8aS)-1,1,4a,6-Tetramethyl-5-[(E)-pent-3-en-1-yl]decahydronaphthalene (192d1)

H

192d1

 188 

191d1’ (132 mg, 0.296 mmol) 192d1 (63,7 mg, 0.243

mmol, 82%) 192d1: white powder; [α]24D = + 31.0 (c = 0.4, CHCl3); FT IR (neat) cm-1;
2923, 2856, 2850; 1H NMR (400 MHz in CDCl3) δ 0.79 (3H, d, J = 8.0 Hz), 0.83 (3H, s), 0.86
(3H, d, J = 8.0 Hz), 1.03-1.61 (13H, m), 1.63 (3H, m), 1.64-2.02 (6H, m), 5.40 (2H, m); 13C
NMR (125 MHz, in CDCl3) δ 15.73, 16.74, 17.86, 18.31, 18.83, 21.96, 26.06, 29.56, 30.05,
31.34, 33.67, 33.89, 35.15, 38.64, 39.87, 41.49, 53.10, 57.04, 124.71, 132.42; HRMS (CI+) m/z
calcd for C19H34 [M]+; 262.2661, found 262.2268.

(4aR,6S,8aS)-1,1,4a,6-Tetramethyl-5-[(E)-pent-2-en-1-yl]decahydronaphthalene(4aR,6S,8aS)-1,1,4a,6-tetramethyl-5-[(Z)-pent-2-en-1-yl]decahydronaphthalene (192d2)
127

and

(E/Z = 4:1)

H

192d2

188



191d2’ (114 mg, 0.255 mmol)192d2 (53.4 mg, 0.204

mmol, 80%) 192d2: white powder; [α]21D = + 16.0 (c = 0.2, CHCl3); FT IR (neat) cm-1;
2995, 2923, 2850; 1H NMR (400 MHz in CDCl3) δ 0.84 (15H, m), 0.95 (3H, t, J = 7.2 Hz),1.04-1.14 (2H, m), 1.32-1.70 (12H, m), 1.86 (2H, m), 1.98 (2H, quin, J = 7.2 Hz), 2.16 (1H, m),
5.25-5.45 (2H, m); 13C NMR (100 MHz in CDCl3) δ (trans) 14.05, 15.25, 16.38, 17.62, 18.49,
21.57, 25.68, 29.14, 29.49, 29.69, 33.31, 33.35, 38.22, 39.57, 42.15, 53.97, 56.75, 129.185,
132.49. (cis) 14.08, 15.38, 16.38, 17.51, 17.95, 21.57, 25.69, 29.10, 29.22, 30.99, 31.90, 34.80,
38.28, 39.57, 42.15, 52.75, 56.69, 124.35, 132.06; HRMS (CI+) m/z calcd for C19H34 [M+H]+;
262.2661, found 262.2657.

4-(Ethoxymethyl)cyclohex-1-ene (192e)

CH2OEt

192e

188



191e’ (121 mg, 0.374 mmol)192e (45.1 mg, 0.322

mmol, 86%) 192e: colorless syrup; FT IR (neat) cm-1; 3023, 2976, 2922, 2854; 1H
NMR (400 MHz in CDCl3) δ 1.97 (3H, t, J = 6.8 Hz), 1.26 (2H, m), 1.72 (1H, m), 1.80-1.93(2H, m), 2.03-2.15 (3H, m), 3.03 (2H, quin, J = 6.4 Hz), 3.48 (2H, q, J = 6.8 Hz), 5.70 (2H, m);
13

C NMR (100 MHz in CDCl3) δ 14.91, 24.29, 25.44, 28.29, 33.56, 66.02, 75.39,125.74,

126.81; HRMS (CI+) m/z calcd for C9H17O [M+H]+; 141.1279, found 141.1279.

(3R*,6R*)-3-Isopropyl-6-methylcyclohex-1-ene (192f)

128

192f

)+@188,95N

1

O191f’ (125 mg, 0.389 mmol)192f (42.4 mg, 0.307

mmol, 79%)2P192f: colorless syrup; FT IR (neat) cm-1; 2958, 2925, 2847; 1H NMR (300
MHz in CDCl3) δ 0.88 (3H, d, J = 6.8 Hz), 0.89 (3H, d, J = 6.8 Hz), 0.96 (3H, d, J = 7.2 Hz),
134-1.55 (3H, m), 1.59-1.71 (1H, br), 1.86 (1H, m), 2.16 (1H, m), 5.58 (2H, m);13C NMR (100MHz, in CDCl3) δ19.78, 19.97, 21.26, 21.98, 28.90, 29.39, 32.18, 41.48, 129.89, 133.46;
HRMS (CI+) m/z calcd for C10H18 [M]+; 138.1409, found 138.1403.

2-(4-Methylcyclohex-3-en-1-yl)propan-2-yl acetate (192g)

OAc
192g

)+@188,95N

1

O191g’ (62.5 mg, 0.318 mmol, 87%)192g (139 mg,

0.366 mmol)2P192g: colorless syrup; FT IR (neat) cm-1; 3313, 3238, 3138, 2957, 2929,
2857, 2856; 1H NMR (400 MHz in CDCl3) d 1.29 (1H, dd, J = 5.6 Hz, 12.0 Hz), 1.41 (3H, s),
1.44 (3H, s), 1.66 (3H, s), 1.76-1.87 (2H, m), 1.93-2.09 (6H, m), 2.21 (1H, m), 2.35 (1H, dt, J =4.4 Hz, 14.0 Hz), 5.37 (1H, dd, J = 1.2 Hz, 2.4 Hz); 13C NMR (100 MHz, in CDCl3) δ 19.99,
22.50, 23.08, 23.81, 25.03, 26.33, 30.84, 37.30, 42.50, 84.84, 120.28, 133.97, 170.52; HRMS(CI+) m/z calcd for C12H19O2 [M-H]+; 195.1385, found 195.1356.

!"*3

8F

182b (129 mg, 0.316 mmol)HD0.1 M 
P:
ITLC

69 (136 mg, 0.474 mmol);LE/(158 μL)0 °C

O1.0 M .);B/JKAG

(O0 °C?<(5.0 mL) =(76P:

O#4
129

O$'

CH2Cl2 (0.85 mL)?<

O0>

10&M76
Boc-(3.0 g)=(

C%

OCBoc

.$-)!
(*

'&5/34(4:1)%5,2"+06#(/34 20:1

188 (31.2 mg, 0.202 mmol, 64%)64 (5.9 mg, 15.6 μmol, 99%)

130

#6

4:1)/1a;` @pl]75o29E
Scheme S1

O

212

K2CO3

O

OAc

2) NaIO4, HIO4
THF/H2O (10:1)
2 h, rt2 steps 90%

S11) PMBCl, NaH
THF, rt, 1 day

OTBS

HO
2) n-BuLi, THF
Paraformaldehyde
12 h -78 °C to rt

S2

MeOH
0 °C to rt, 8 h
90%1) TBSCl
Imidazole
DMF, 1 h, rtOH(OMe)2N21) mCPBA
CH2Cl2, 3 h, 0 °C

OAc

O
P

S3

2 steps 87%

2) TBAF
THF, 8 h, rt3) Ac2O, Pyridine
8 h, rt3steps 82%

OR

214: R = TBS (4 eq)
215: R = TBDPS(10 eq)ClMg
OAc

Li2CuCl4(0.4 eq)
THF/Et2O (1:2)
15 min, 0 °C

O

PMBO

(PMB基)

216: R = TBS>99%
72 : R = TBDPS 98%

213

MeO

OR

 hi)$/+ (212) (200 g, 1.02 mol)CH2Cl2 (2.5 L)Wgr0 ℃m-CPBA(>65%cAr228 g, 1.02 mmol)CH2Cl2 (2.5 L)WR4IkGFrm>OS9[3\, e^Orn:m>OPQ

X0s VAs BrKL_1.0 M Oi7OWR(×2)

sMrKL_MgSO41Z

rT=Y

dr8DNU!*+,(")%/(& -tAcOEt = 8t1)bf
'!#C(199 gr0.938 mol, 92q)sMr'!#(199 g, 0.938 mol)THF

e^O(10:1, 2.2 L)S9W?Wgr0 ℃NaIO4 (120 g, 0.563 mol)HIO4.2H2O(235 g, 1.03 mol)H<4
9[6

s

X0

s

VA1IkGFrm>OSBrKL_n:jJOWR(×2)r, e^Orn:m>O
131

Z[

{WzUVjMgSO4<e81)"5.:(/z_Gcm$9: AcOEt = 5:1)lq

zBPX`%6#7!

S1O

S11H,13C-NMRLtFAnSg64bHD;o WzS1 (156 g, 0.938 mol)MeOH(1.8 L)br(156 gz0.938 mol, 98y){ksz0 ℃du63(259 g, 1.78
z 0 °CKamol)dimethyl 1-diazo-2-oxopropylphosphonate (216 g, 1.12 mol)^?
N?a8TvRQ{

MzbJcm

VjI@94+3Yb\xEwIYZ[
e
lq

z_Gcm

ks

{WzUVjMgSO4<$9}AcOEt = 3:1)

(105 gz0.844 mol, 90y). S2 1H,13C-NMRAnSg64b;o{ WzS2 (36.0 g, 290 mol)DMF(580 mL)br2'&:7 (59.2 mg, 870 mmol)^?
AcOEt (4:1)]CbJpiY?
WzUVjMgSO4<e.:(/zEt2OpiY?zU

zBPX`%6#7!81)"5.:(/

S2O

{

{Ka1TvRQ

z/

$9

{UVjpiYxEwIYZ[

{

z_Gcm

$9}AcOEt = 20}1)lq

z0 ℃TBSCl (52.5 g, 349 mmol)zBPX`%6#7!81)"5

TBS=O(65.8 g, 276 mmol, 95%). TBS=; FT IR (neat) cm-1; 3313, 2956, 2930, 2889, 2858; 1H NMR (300 MHz in CDCl3) δ 0.67 (6H,s), 0.90 (9H, s), 1.64 (3H, t, 1H, J = 0.3 Hz), 1.95 (1H, t, J = 2.7 Hz), 2.28 (4H, m), 4.20 (2H,
ddd, J = 0.9 Hz, 1.8 Hz, 6.3 Hz), 5.35 (1H, m); 13C NMR (75 MHz, in CDCl3) δ -5.17, 16.05,
17.16, 18.26, 25.89, 38.09, 60.03, 68.56, 83.78, 125.62, 134.74; MS (CI+) m/z 238 [M]+; HRMS(CI+) C14H26OSi m/z calcd for 238.1753, found 238.1725.
 WzTBS= (64.0 g, 268 mmol)THF (895 mL)br$9b\z251 mL, 402 mmol)?

, -78℃n-BuLi (1.6 M /{]Cf-78℃|TvRQ

z,50737(-* (12.1 g, 402 mmol)THFb\(50 mL)-78℃]Cf?

{0 °CKa

N?a12TvRQ

MzBPfI@94+3Yb\>hUVjI@94+3Yb\(×2)xEwIYZ[
MgSO4<ez_Gcm

AcOEt = 8:1)lq{WzUVjzBPX`%6#7!81)"5.:(/

S3O

{

$9}

(66.3 g, 247 mmol, 92%){S3; FT IR (neat) cm-1; 3431,

2957, 2926, 2857, 2286, 2223, 1671; 1H NMR (300 MHz in CDCl3) δ 0.75 (6H, s), 0.90 (9H, s),132

1.62 (3H, s), 2.21 (2H, t, J = 6.9 Hz), 2.33 (4H, m), 4.21 (4H, m), 5.36 (1H, ddd, J = 1.8 Hz, 2,7
Hz, 6.9 Hz); 13C NMR (75 MHz, in CDCl3) δ -5.27, 15.96, 17.36, 18.24, 25.82, 38.08, 50.70,
60.09, 79.06, 85.12, 125.23, 135.11; MS (CI+) m/z 269 [M+H]+; HRMS (CI+) C15H29O2Si m/z
calcd for 269.1937, found 269.1932.
 NjS3 (66.0 g, 246 mmol)THF (820 mL)Xe
19.7 g, 492 mmol)I>8

9

, 0 ℃NaH (60%1FY\jkT<\0 ℃lKgHG*3#120% (50 mL, 369 mmol)0 ℃T<\9
9W

12KgHG

Bj;E\Et2Oc_P7^

3.&,PXS(×2)i=h@PQR
 jU?Zbdk BjLM`@:kNj;EOV (64.0 g, 268 mmol)THF (250 mL)Xe

j;E\Et2O@:3.&,PXS7^

PXS(×2)i=h@PQRb

k0 °CAWCkNjLM`MgSO45[

TBAF (1.0 M THFXSj369 mL, 369 mmol)0 °C9
G

j'/-$#

j;EOV#0,0℃

kT<\AW8KgH

kLM`@:3.&,kNjLM`MgSO45[jU?Z

12+$/(4()"3mAcOEt = 8:12:1)afJ1]1!416D(54.0 g, 197 mmol, 80%)k1!416; FT

IR (neat) cm-1; 3431, 2957, 2926, 2857, 2286, 2223, 1671; 1H NMR (500 MHz in CDCl3)
δ 1.24 (OH, t, J = 7.0 Hz), 1.70 (3H, s), 2.26 (2H, t, J = 7.0 Hz), 2.38 (2H, m), 3.81 (3H, s),4.10 (2H, d, J = 2.0 Hz), 4.15 (2H, d, J = 7.0 Hz), 4.51 (2H, s), 5.48 (1H, dt, J = 1.0 Hz, 7.0Hz),6.78 (2H, m), 7.27 (2H, m); 13C NMR (125 MHz, in CDCl3) δ 16.08, 17.62, 38.28, 55.29, 57.30,
59.31, 71.02, 76.66, 86.26, 113.81, 127.72, 129.65, 129.75, 137.76, 159.35; MS (CI+) m/z 269[M+H]+; HRMS (CI+) C15H29O2Si m/z calcd for 269.1937, found 269.1932.

(E)-8-[(4-Methoxybenzyl)oxy]-3-methyloct-2-en-6-yn-1-yl acetate (213)OAc

O(PMB基)
MeO

213

133

 D

d(+(.(50.0 g, 182 mmol)'*(360 mL)(51.6 mL, 546 mmol)0 °C 3eJ6S:N
9`

O\, 0 ℃

QF_`

8Aa@?d5=SEt2O/TeBCV1 M 9`(×2)YUFdc7b9FGHeD

,RdL8PXd5=EM'()"&

BCVMgSO4

*:AcOEt = 4:1) W[

1M
d

+(!

213<(57.6 g, 182 mmol, quant)e213: FT IR (neat) cm-1;

2997, 2938, 2912, 2853, 1739; 1H NMR (500 MHz in CDCl3) δ 1.73 (3H, s), 2.03 (3H, s), 2.39
(2H, dt, J = 1.5 Hz, 3.5 Hz), 3.80 (3H, m), 4.11 (2H, t, J = 2.5 Hz), 4.51 (2H, s), 4.59 (2H, d, J
= 7.0 Hz), 5.41 (1H, dt, J = 1.5 Hz, 6.0Hz), 6.88 (2H, dd, J = 1.5 Hz, 8.5 Hz), 7.27 (2H, dd, J =1.5 Hz, 8.5 Hz); 13C NMR (125 MHz, in CDCl3) δ 16.29, 17.54, 21.00, 38.29, 55.27, 57.25,
61.19, 70.94, 76.58, 86.12, 113.79, 119.50, 129.56, 129.74, 140.27, 159.33, 171.05; MS (CI+)
m/z 315 [M-H]+; HRMS (CI+) C19H23O4 m/z calcd for 315.1596, found 315.1578.

(E)-t-Butyl{3-{9-[(4-methoxybenzyl)oxy]-4-methylnon-3-en-7-yn-1-yl}phenoxy}dimethylsilane (216)
OTBS

PMBO

216

213 (25.0 g, 79.0 mmol) THF (79 mL)O\d0 ℃

mmol, 316mL)K3eJ6S 0 ℃
Z 21481)

Li2CuCl4

0.1 M THF OI(31.6

15 1a@?d-2^['%]

0.75 M Et2O (316 mL, 237 mmol)OI 0 ℃

;d5=Sc794*$#FOI

3e0 ℃

/TeBCS Et2O

794*$#FOI(×2)dYUF(×2)c7b9F
CV MgSO4

W[

>0dc

GHeD

,RdL8PXdEM'()"&*fAcOEt = 30:1)

15 1a@?

dB

+(!

216 (37.8 g, 79.0 mmol, quant)<e216; colorless syrup; FT

IR (neat) cm-1; 2953, 2930, 2856, 1602, 1584; 1H NMR (500 MHz in CDCl3) δ 0.19 (6H, s),
0.97 (9H, s), 1.57 (3H, s), 2.20 (1H, t, J = 7.5 Hz), 2.31 (3H, m), 2.57 (2H, t, J = 7.5 Hz), 3.80
(3H, s), 4.11 (2H, t, J = 2.0 Hz), 4.51 (2H, s), 4.59 (2H, d, J = 7.0 Hz), 5.24 (1H, dt, J = 1.0 Hz,
134

7.0Hz), 6.54 (2H, m), 6.76 (1H, d, J = 7.0 Hz), 6.87 (2H, dt, J = 2.0 Hz, 7.0 Hz), 7.11 (1H, dt, J= 2.0 Hz, 7.0 Hz), 7.28 (2H, m); 13C NMR (125 MHz, in CDCl3) δ -4.39, 15.81, 18.01, 18.21,
25.72, 29.82, 35.86, 38.62, 55.28, 57.32, 70.89, 76.18, 86.84, 113.78, 117.35, 130.24, 125.51,
124.85, 129.03, 129.72, 129.77, 134.15, 143.79, 155.54, 159.30; HRMS (CI+) m/z calcd for
C30H42O2Si [M]+; 478.2903, found 478.2908.
(E)-tert-Butyl{3-{9-[(4-methoxybenzyl)oxy]-4-methylnon-3-en-7-yn-1-yl}phenoxy}diphenyl
silane (72)OTBDPS

72

PMBO

216

"

$ 213 (25.0 g, 79.0 mmol)

72 (46.7 g, 77.4 mmol, 98%)

21564b) (0.6 M THF '%, 237 mL, 395 mmol)

072: colorless syrup; FT IR (neat) cm-1; 3070, 3048,

3029, 2998, 2931; 1H NMR (400 MHz in CDCl3) δ 1.10 (9H, s), 1.50 (3H, s), 2.11 (2H, q, J =7.6 Hz), 2.17 (2H, t, J = 7.6 Hz), 2.29 (2H, m), 2.44 (2H, t, J = 7.2 Hz), 3.79 (3H, s), 4.11 (2H, t,
J = 2.0 Hz), 4.51 (2H, s), 5.14 (1H, dt, J = 1.2 Hz, 7.6 Hz), 5.56 (1H, ddd, J = 0.8 Hz, 2.8 Hz,
8.0 Hz), 6.60 (1H, t, J = 1.6 Hz), 6.66 (1H, d, J = 8.0 Hz), 6.87 (2H, dt, J = 1.6 Hz, 8.8 Hz),6.96 (1H, t, J = 8.0 Hz), 7.27 (2H, m), 7.33-7.44 (6H, m), 7.71 (4H, m); 13C NMR (100 MHz, in
CDCl3) δ 15.76, 18.00, 19.49, 26.56, 29.68, 35.77, 38.58, 55.28, 57.32, 70.96, 76.16, 86.87,
113.78, 117.02, 119.82, 121.27, 124.81, 127.72, 128.80, 129.70, 129.77, 129.83, 133.08, 134.04,
135.53, 143.56, 155.49, 159.29; HRMS (CI+) m/z calcd for C40H46O3Si [M]+; 602.3216,
found 602.3219.

0.1 M #-+(C2B10H11HgCl/AgOTf) ,*64 (2.28 g, 6.01 mmol) 0.1 M (#CH2Cl2 (60 mL)'% /AgOTf (1.54 g, 5.99 mmol)
0 °C/&30.

0!135'%

)0Oridamycin A T4)/9(±)-(4bS,8aR)-8-{[(4-Methoxybenzyl)oxy]methyl}-4b-methyl-4b,5,6,8a,9,10-hexahydrophe
nanthren-2-ol (73)
OH

H
PMBO

73

 72 (20.8 g, 34.5 mmol) CH2Cl2 (345 mL)JS, 0 ℃
 0.1 M CH2Cl2 (34.5 mL, 3.45 mmol)JE 0 °C
3 =V<;Z.8MY0X3B
3 1:+[@*N

Z>?O MgSO4(34.5 mL)JS, 0 ℃-

m-C2B10H11HgCl/AgOTf (1:1)[[>?O,W

B

6Z>?O MgSO4

$%!"'(F/M

ZBO CH2Cl2[.8AH THF

TBAF (1.0 M THF JEZ51.8 mL, 51.8 mmol) 0 °C

1 =V<;Z.8M Et2O  1 M 3U[



(LZG2KQ

F/M 0 °C
CDI5-[*NZ>?OY0X3(LZG2KQZ.8AH#&\AcOEt = 8:1  3:1)

mmol, 80%) 64 (1.26 g, 3.32 mmol, 96%)7PR

73 (10.1 g, 27.7

[73; white syrup; FT IR (neat) cm-1; 3340,

2935, 2911, 2862, 2829; 1H NMR (500 MHz in CDCl3) δ 1.01 (3H, s), 1.64 (3H, m), 2.13 (1H,m), 2.24 (2H, d, J = 4.8 Hz), 2.41 (1H, dt, J = 2.5 Hz, 13.5 Hz), 2.85 (2H, m), 3.80 (3H, s), 3.86
(2H, d, J = 11.5 Hz), 4.10 (1H, d, J = 11.5 Hz), 4.39 (1H, d, J = 11.5 Hz), 4.46 (1H, d, J = 11.5
Hz), 5.01 (OH, br s), 5.75 (1H, d, J = 2.5 Hz), 6.53 (1H, d, J = 2.5 Hz), 6.60 (1H, dd, J = 3.0 Hz,
8.5 Hz), 6.87 (2H, dt, J = 2.5 Hz, 9.0 Hz), 7.16 (1H, d, J = 8.5 Hz), 7.25 (2H, dt, J = 2.5 Hz, 9.0
Hz); 13C NMR (125 MHz, in CDCl3) δ 20.00, 22.31, 23.23, 29.27, 33.38, 35.35, 42.14, 55.29,
55.27, 71.14, 72.84, 112.60, 113.75, 115.37, 125.38, 126.46, 129.51, 130.49, 135.16, 137.13,
139.51, 152.28, 159.10; HRMS (CI+) m/z calcd for C24H28O3 [M]+; 364.2038, found 364.2045.

136

(±)-(4bS,8aR)-8-{[(4-Methoxybenzyl)oxy]methyl}-4b-methyl-4b,5,6,8a,9,10-hexahydrophe
nanthren-4-ol (217)
HO

H
PMBO

73

217

(#,

216 (1.00 g, 2.09 mmol) 73 (456 mg, 1.25 mmol, 60%)

0.418 mmol, 20%)"217(152 mg,?217; white syrup; FT IR (neat) cm-1; 3344, 2958, 2937, 2903, 2875,

2834; 1H NMR (300 MHz in CDCl3) δ 1.22 (3H, s), 1.56 (3H, m), 2.09 (1H, ddt, J = 1.8 Hz, 6.0
Hz, 10.8 Hz), 2.23 (2H, m), 2.52 (1H, d, J = 12.9 Hz), 2.88 (2H, m), 3.22 (1H, dd, J = 4.5 Hz,
12.9 Hz), 3.80 (3H, s), 3.90 (1H, d, J = 11.4 Hz), 4.07 (1H, d, J = 11.4 Hz), 4.42 (1H, d, J =11.4 Hz), 4.47 (1H, d, J = 11.4 Hz), 4.95 (OH, s), 5.75 (1H, d, J = 3.0 Hz), 6.44 (1H, dd, J = 2.5
Hz, 4.8 Hz), 6.68 (1H, dd, J = 0.9 Hz, 7.8 Hz), 6.88 (2H, dt, J = 2.7 Hz, 8.9 Hz), 6.94 (1H, t, J =7.8 Hz), 7.27 (2H, dt, J = 2.7 Hz, 8.7 Hz); 13C NMR (75 MHz, in CDCl3) δ 17.10, 19.79, 23.81,
31.66, 32.04, 37.01, 45.15, 55.29, 71.13, 73.14, 113.74, 113.79, 122.77, 126.18, 127.33, 129.50,
130.64, 132.86, 134.94, 138.95, 154.61, 159.08; HRMS (CI+) m/z calcd for C24H28O3 [M]+;364.2038, found 364.2039.

(±)-(4bS,8aR)-8-{[(4-Methoxybenzyl)oxy]methyl}-4b-methyl-4b,5,6,8a,9,10-hexahydrophe
nanthren-2-yl trifluoromethanesulfonate (218)
OTf

H
PMBO

218

 73 (10.0 g, 27.4 mmol) CH2Cl2 (274 mL)2:>0 ℃
4+(6.9 mL, 41.1 mmol)/+
5?')796+>038

=<218 "

+

?!1

-.

(11.0 mL, 137 mmol)
1 &;%$

?*



>96

>')7 MgSO4

(13.6 g, 27.4 mmol, quant). 218: pale yellow oil; FT
137

IR (neat) cm-1; 2936, 2857, 2838; 1H NMR (300 MHz in CDCl3) δ 1.03 (3H, s), 1.64 (3H, m),
2.25 (4H, m), 2.42 (1H, dt, J = 3.0 Hz, 13.5 Hz), 2.96 (2H, dd, J = 4.8 Hz, 8.7 Hz), 3.80 (3H, s),
3.86 (1H, d, J = 11.4 Hz), 4.09 (1H, d, J = 11.4 Hz), 4.41 (1H, d, J = 11.4 Hz), 4.43 (1H, d, J =11.4 Hz), 5.77 (1H, d, J = 2.7 Hz), 6.88 (2H, dt, J = 1.0 Hz, 8.7 Hz), 6.98 (1H, t, J = 2.4 Hz),7.01 (1H, dd, J = 2.7 Hz, 8.4 Hz), 7.26 (1H, dd, J = 1.0 Hz, 8.7 Hz), 7.36 (1H, d, J = 8.7 Hz);13

C NMR (75 MHz, in CDCl3) δ 19.68, 22.18, 23.05, 29.20, 33.13, 35.96, 41.54, 55.28, 71.35,

72.77, 113.76, 118.03, 121.43, 126.10, 126.26, 129.49, 134.90, 138.49, 147.38, 147.54, 159.10;
HRMS (CI+) m/z calcd for C24H27F3O3S [M]+; 496.1531, found 496.1530.

Buchwald-Hartwig  (Table S2)Table S2
OTfAniline (1.5 eq)
Cs2CO3, Pd(OAc)2
Ligand

NH
PPh2
PPh2

Toluene, reflux

H
PMBO

H

218

Entry

PMBO

Pd(OAc)2(mol%)

Ligand(mol%)

Cs2CO3
(eq)

Time

219

BINAP

Product (%)a

i-Pr
Cy2P

i-Pr

1c

20

XPhos (30)

1.2

24 h

5 (27)b2

20

XPhos (30)

3.0

3h

77

3

20

XPhos (30)

5.0

3h

97

4

20

PPh3 (30)

5.0

24 h

66

5

20

(±)-BINAP (30)

5.0

3h

21

6

20

SPhos (30)

5.0

3h

quant.

OMe

7

10

SPhos (15)

5.0

12 h

98

SPhos

i-Pr
XPhos

OMe
Cy2P

a Isolated yield. b Recovery of SM. c cf) J. Org. Chem. 2009, 74, 4720-4726.

218 (0.1 mmol), (0.15 mmol)



(Entries 1-7).

138(1.0 mL)

(±)-(4bS,8aR)-8-{[(4-Methoxybenzyl)oxy]methyl}-4b-methyl-N-phenyl-4b,5,6,8a,9,10-hexa
hydrophenanthren-2-amine (219)

NH

H
PMBO

219

218 (13.6 g, 27.4 mmol)

EKC#%(91 mL)>GM/=

41.1 mmol)M@K(44.6 g, 137 mmol)MPd(OAc)2 (615 mg, 2.74 mmol)MSPhos (1.69

g, 4.11 mmol)

"%(3.75 mL,:+N+AI86('M3 5L43M/=),M

"#

HMJK#2*N 9

#$!

;.?DM-17<&(%OAcOEt = 10:1)BF 219

"

0(11.8 g, 26.9

mmol, 98%). 219: colorless syrup; FT IR (neat) cm-1; 3389, 3031, 2953, 2932, 2907; 1H NMR(300 MHz in CDCl3) δ 1.05 (3H, s), 1.67 (3H, m), 2.16 (1H, ddd, J = 3.6 Hz, 6.3 Hz, 13.2 Hz),2.26 (2H, m), 2.65 (1H, dt, J = 1.0 Hz, 12.9 Hz), 2.89 (2H, m), 3.80 (3H, s), 3.86 (1H, d, J =11.7 Hz), 4.10 (1H, d, J = 11.7 Hz), 4.90 (1H, d, J = 11.4 Hz), 4.92 (1H, d, J = 11.4 Hz), 5.59
(NH, s), 5.76 (1H, d, J = 1.0 Hz), 6.87 (5H, m), 7.07 (2H, m), 7.24 (5H, m); 13C NMR (75 MHz,in CDCl3) δ 20.12, 22.33, 23.29, 29.49, 32.41, 35.53, 42.28, 55.30, 71.24, 72.91, 113.75,
115.83, 117.31, 118.53, 120.39, 125.13, 126.19, 129.23, 129.41, 130.68, 135.36, 136.69, 140.41,
140.45; HRMS (CI+) m/z calcd for C30H33NO2 [M]+; 439.2511, found 439.2508.

(±)-N-{(4bS,8aR)-8-{[(4-Methoxybenzyl)oxy]methyl}-4b-methyl-4b,5,6,8a,9,10-hexahydrop
henanthren-2-yl}-N-phenylbenzenesulfonamide

N

O
S O

H
PMBO

220

139

 219 (10.3 g, 23.4 mmol)%.1(78 mL)P[a0 ℃(11/*$/0.

"(8.97 mL, 70.2 mmol)L5

b;O

aDEVYUH`8_:H

18 B^A@IJ

bF

aEt2O  1 M :\5

aDEV MgSO4

M9QX./0+!-&2('1cAcOEt = 5:1)

3Ra

WZ

220 >(14.6 g, 22.2 mmol, 94%). 220: colorless syrup; FT IR (neat) cm-1; 3064, 3031, 2958, 2934,
2852; 1H NMR (400 MHz in CDCl3) δ 1.01 (3H, s), 1.23 (2H, m), 1.63 (3H, m), 2.24 (3H, m),
2.40 (1H, d, J = 13.2 Hz), 2.85 (2H, m), 3.80 (3H, s), 3.85 (1H, d, J = 11.2 Hz), 4.07 (1H, d, J =11.2 Hz), 4.37 (1H, d, J = 11.2 Hz), 4.43 (1H, d, J = 11.2 Hz), 5.75 (1H, s), 6.87 (2H, dt, J = 2.8
Hz, 8.4 Hz), 6.98 (2H, m), 7.24 (8H, m), 7.48 (2H, t, J = 8.0 Hz), 7.59 (1H, dt, J = 1.2 Hz, 6.8
Hz), 7.72 (2H, m); 13C NMR (100 MHz, in CDCl3) δ 19.86, 22.15, 23.14, 29.11, 33.11, 35.5,
41.71, 55.28, 71.27, 72.83, 113.75, 125.10, 125.20, 126.15, 127.39, 127.82, 129.09, 129.18,
129.39, 130.58, 132.65, 135.13, 136.89, 138.60; HRMS (CI+) m/z calcd for C36H37NO4S [M]+;579.2443, found 579.2446.

(±)-N-[(4bS,8aR)-8-Formyl-4b-methyl-4b,5,6,8a,9,10-hexahydrophenanthren-2-yl]-N-phenylbenzenesulfonamide (221)

NBs

OHC

H
221

 220 (10.3 g, 23.4 mmol) CH2Cl2/H2O(10:1, 240 mL)P[a0 ℃mmol)L5

b0 °C ;O=5Oa18 B^A@]CH5aDEVYUH`8_:H
3RaM9QX

bF

IJ

bCH2Cl2 `8aDEV MgSO4

a6?GN CH2Cl2 (206 mL)P[, 0 ℃21)/,2#1 (18.74 g, 20.6 mmol) 0 °C
@a6?S CH2Cl2 `8]CH<aDEV MgSO4bF

DDQ (7.03 g, 31.05

bK7S;O

4TaDEV`8_:H

IJ

+
1 B^A
b



3RaM9QXa./0+!-&2('140

!IAcOEt = 8:1)

?B 221 -(10.2 g, 19.0 mmol, 92%). 221: colorless syrup; FT

IR (neat) cm-1; 3064, 2963, 2920, 2833, 2718, 2257, 1682; 1H NMR (400 MHz in CDCl3)
δ 1.01 (3H, s), 1.56 (2H, m), 2.33 (1H, dt, J = 3.6 Hz, 12.8 Hz), 2.53 (3H, m), 2.95 (3H, m),
6.83 (1H, d, J = 2.8 Hz), 6.96 (1H, d, J = 3.0 Hz), 7.03 (1H, dd, J = 2.0 Hz, 8.4 Hz), 7.26 (6H,m), 7.48 (2H, t, J = 7.6 Hz), 7.60 (1H, dt, J = 7.6 Hz), 7.70 (2H, d, J = 7.6 Hz), 9.48 (1H, m);
13

C NMR (100 MHz, in CDCl3) δ 18.60, 22.07, 24.61, 28.42, 31.85, 35.66, 40.06, 124.58,

125.32, 127.44, 128.41, 128.84, 129.08, 132.70, 136.97, 140.61, 141.45, 141.33, 145.71, 152.46,
194.63; HRMS (CI+) m/z calcd for C28H27NO3S [M]+; 457.1712, found 457.1699.

(±)-N-[(4bS,8S,8aR)-8-Formyl-4b,8-dimethyl-4b,5,8,8a,9,10-hexahydrophenanthren-2-yl]N-phenylbenzenesulfonamide (222)

NBs

OH
C

H

222

 221 (8.25 g, 15.4 mmol)!(154 mL) 9CG,8mmol)6'H80 °Cmmol)'H$=3

1 0D/.

G80 °C

1 0D/.

&<H12>F)E+3



G,8

%( MeI (19.2 mL, 308

G,8

45GMgSO4

"(!IAcOEt = 8:1)

t-BuOK (6.90 g, 61.5%(

 Et2OA#;G7*:@?B 222 -(5.76 g, 10.5mmol, 68%). 222: white powder; FT IR (neat) cm-1; 3063, 3024, 2966, 2933, 2872, 1717; 1H
NMR (400 MHz in CDCl3) δ 1.13 (3H, s), 1.23 (3H, s), 1.82 (2H, m), 2.15 (2H, m), 2.56 (1H,
dd, J = 2.0 Hz, 17.2 Hz), 2.81 (2H, m) 5.66 (1H, dd, J = 2.8 Hz, 10.0 Hz), 5.91 (1H, ddd, J =2.0 Hz, 5.6 Hz, 10.0 Hz), 6.96 (1H, d, J = 2.4 Hz), 7.01 (1H, dd, J = 2.4 Hz, 8.4 Hz), 7.29 (5H,m), 7.48 (2H, t, J = 8.0 Hz), 7.56 (2H, dt, J = 1.2 Hz, 6.8 Hz), 7.70 (1H, d, J = 1.2 Hz, 6.8 Hz),9.81 (1H, s); 13C NMR (100 MHz, in CDCl3) δ 19.60, 23.14, 25.31, 31.15, 36.62, 39.75, 49.94,
50.43, 125.89, 127.06, 127.28, 127.47, 127.74, 128.39, 128.63, 128.89, 129.20, 129.66, 132.71,
141136.12, 138.73, 140.56, 141.35, 145.66, 204.87; HRMS (CI+) m/z calcd for C29H29NO3S [M]+;471.1868, found 471.1867.

(±)-Methyl(1S,4aS,10aR)-1,4a-dimethyl-7-(N-phenylphenylsulfonamido)-1,4,4a,9,10,10a-he
xahydrophenanthrene-1-carboxylate (223)

NBs

MeO2C

H

223

222 (2.76 g, 5.85 mmol)

THF/t-BuOH (1:1, 30 mL)

6?9 (4.57 g/30 mL, 29.3 mmol)0/PEt2O

IE6

BP<(@HQ4

NaClO2(1.99g, 17.6 mmol)#DQ23F

P%.5=

Q



/AcOEt (4:1) IE6,P23F

!(MgSO4

RAcOEt = 6:1)

?KP0 °C

NaH2PO4;$Q+>

1 1M

O'N)6

DMF (20 mL)

58.5 mmol) AL (4.04 g, 29.3 mmol)
%.C

:&?*

?K, +>$Q:&C#DP23F

78PMgSO4

80 °C

IE6

"

MeI (3.64 mL,
1 1M0/P

O'N)6

78

"BP<(@HP

GJ 223-(3.29 g, 5,67 mmol, 97%). 223: white

powder; FT IR (neat) cm-1; 3064, 3025, 2921, 2880, 2838, 1726; 1H NMR (500 MHz in CDCl3)
δ 1.10 (3H, s), 1.36 (3H, s), 1.69 (1H, dd, J = 1.0 Hz, 10.0 Hz), 1.84 (1H, dd, J = 5.5 Hz, 13.5
Hz), 2.08 (1H, d, J = 17.5 Hz), 2.23 (1H, dd, J = 5.0 Hz, 13.5 Hz), 2.49 (1H, dd, J = 2.5 Hz,
17.5 Hz), 2.67 (1H, dt, J = 2.0 Hz, 12.5 Hz), 2.80 (1H, dd, J = 3.0 Hz, 13.0 Hz), 3.63 (3H, s),5.72 (2H, m), 6.93 (1H, d, J = 2.0 Hz), 7.01 (1H, dd, J = 2.0 Hz, 8.5 Hz), 7.16 (1H, d, J = 8.5
Hz), 7.25 (5H, m), 7.46 (2H, t, J = 7.0 Hz), 7.57 (1H, t, J = 7.0 Hz), 7.70 (2H, d, J = 7.0 Hz);13

C NMR (125 MHz, in CDCl3) δ 20.84, 23.45, 23.51, 27.54, 31.41, 36.66, 40.26, 45.03, 49.87,

51.59, 124.38, 125.72, 127.27, 127.34, 127.65, 128.28, 128.42, 128.75, 129.10, 131.41, 132.63,
136.59, 138.37, 140.47, 141.34, 146.23, 175.94; HRMS (CI+) m/z calcd for C30H33NO7S [M]+;501.1974, found 501.1978.
142

(±)-Methyl(6aR,7R,7aS,8aR,9aS)-7,9a-dimethyl-3-(N-phenylphenylsulfonamido)-5,6,6a,7,7
a,8a,9,9a-octahydrophenanthro[2,3-b]oxirene-7-carboxylate (224)

NBs

O
MeO2C

H

224

223 (2.60g, 5.18 mmol)
mmol)

THF (52 mL)=GL0 °C  m-CPBA (D.>65%, 6.88 g, 25.9:&M50 °C  24 2I10'5=8%AM34B;+>EL10%?H
AcOEt = 6:1)CF 224

L-<

$( Et2O

1 M 5HK*J,567LMgSO4 #@L9)"(!N/(2.55 g, 4.92 mmol, 95%). 224: white powder; FT IR(neat) cm-1; 3064, 2967, 2945, 2912, 2885, 2839, 1718; 1H NMR (400 MHz in CDCl3) δ 1.10
(3H, s), 1.48 (3H, s), 1.66 (1H, d, J = 12.8 Hz), 1.72 (1H, dq, J = 4.8 Hz, 11.2 Hz), 1.88 (1H, d,
J = 15.2 Hz), 2.12 (1H, dd, J = 4.4 Hz, 12.8 Hz), 2.43 (1H, dd, J = 6.0 Hz, 15.2 Hz), 2.74 (1H,m), 3.41 (1H, dd, J = 4.0 Hz, 5.6 Hz), 3.56 (1H, d, J = 4.0 Hz), 3.70 (3H, s), 6.89 (1H, d, J = 2.4
Hz), 7.01 (1H, dd, J = 2.4 Hz, 8.4 Hz), 7.11 (1H, d, J = 8.4 Hz), 7.26 (5H, m), 7.47 (2H, t, J =7.6 Hz), 7.58 (1H, tt, J = 1.6 Hz, 7.6 Hz), 7.67 (2H, m); 13C NMR (100 MHz, in CDCl3) δ 20.17,
23.80, 25.22, 31.65, 36.07, 38.90, 43.96, 44.06, 51.69, 52.73, 57.71, 125.87, 127.41, 127.72,
128.27, 128.31, 128.82, 129.18, 132.69, 136.66, 138.53, 140.50, 141.36, 145.79, 176.00; MS
HRMS (CI+) m/z calcd for C30H32NO5S [M+H]+; 518.2001, found 518.2007.

(±)-Methyl(1R,4aS,10aR)-1,4a-dimethyl-2-oxo-7-(N-phenylphenylsulfonamido)-1,2,3,4,4a,9,10,10a-octahydrophenanthrene-1-carboxylate (229)

143

NBs

O
MeO2C

H

229

#%(9.6 mL)

224 (1.00 g, 1.93 mmol)>GL0 °C  2,6-#% (1.12 mL, 9.65mmol)LTMSOTf (1.05 mL, 5.79 mmol)LTMSBr (764 μL, 5.79 mmol) <+M+@H
9 24 4I32

L0 °C

0 °C  15 *I32

(- TBAF (15.4 mL, 15.4 mmol) <+M

LEt2O K.0,%

7>;)BM56C

K.J078:LMgSO4 'AL=/?EL"#$!
&(%NAcOEt = 4:1)DF 229

1(921 mg, 1.78 mmol, 92%). 229:

colorless syrup; FT IR (neat) cm-1; 3059, 2959, 2926, 2861, 1712; 1H NMR (500 MHz in
CDCl3) δ 1.28 (3H, s), 1.48 (3H, s), 1.75 (2H, m), 2.13 (2H, s), 2.49 (1H, ddd, J = 2.0 Hz, 6.0
Hz, 13.0 Hz), 2.56 (1H, dq, J = 2.0 Hz, 15.0 Hz), 2.76 (1H, m), 2.87 (1H, dt, J = 3.0 Hz, 17.0Hz), 3.10 (1H, dt, J = 6.0 Hz, 13.0 Hz), 3.70 (3H, s), 6.96 (1H, d, J = 2.0 Hz), 7.01 (1H, dd, J =2.0 Hz, 8.5 Hz), 7.19 (1H, d, J = 8.5 Hz), 7.26 (3H, m), 7.31 (2H, m), 7.48 (2H, t, J = 7.5 Hz),7.60 (1H, t, J = 7.5 Hz); 13C NMR (125 MHz, in CDCl3) δ 20.88, 21.13, 22.57, 31.55, 37.29,
37.89, 38.85, 52.25, 53.52, 57.40, 125.73, 126.45, 127.78, 128.97, 128.76, 128.88, 129.26,
132.76, 136.35, 139.14, 140.57, 141.32, 145.41, 173.91, 207.63; HRMS (CI+) m/z calcd for
C30H31NO5S [M]+; 517.1923, found 517.1914.

(±)-Methyl(1R,2S,4aS,10aR)-2-hydroxy-1,4a-dimethyl-7-(phenylamino)-1,2,3,4,4a,9,10,10a-octahydrophenanthrene-1-carboxylate (233)

NH

HO
MeO2C

H

233

144

229 (776 mg, 1.50 mmol)(720 mg, 30.0 mmol)EO

Q\d=P'

M3e40 °C  6 BaA@

Et2O c7:4

eCDV

Et2O/)!0-(1:1, 40 mL)/*(GQK

dQ;

M3CDVRZe5?

c7b:GHJ

MgSO4 2UdN8RZd10%S`,(-.'+%0(&/fAcOEt = 2:1)Y[ 233

(XL6,>(507 mg, 1.40 mmol,93%). 233: colorless syrup; FT IR (neat) cm-1; 3059, 2959, 2926, 2861, 1712; 1H NMR (500
MHz in CDCl3) δ 1.28 (3H, s), 1.48 (3H, s), 1.75 (2H, m), 2.13 (2H, s), 2.49 (1H, ddd, J = 2.0
Hz, 6.0 Hz, 13.0 Hz), 2.56 (1H, dq, J = 2.0 Hz, 15.0 Hz), 2.76 (1H, m), 2.87 (1H, dt, J = 3.0 Hz,
17.0 Hz), 3.10 (1H, dt, J = 6.0 Hz, 13.0 Hz), 3.70 (3H, s), 6.96 (1H, d, J = 2.0 Hz), 7.01 (1H, dd,
J = 2.0 Hz, 8.5 Hz), 7.19 (1H, d, J = 8.5 Hz), 7.26 (3H, m), 7.31 (2H, m), 7.48 (2H, t, J = 7.5
Hz), 7.60 (1H, t, J = 7.5 Hz); 13C NMR (125 MHz, in CDCl3) δ 20.88, 21.13, 22.57, 31.55,
37.29, 37.89, 38.85, 52.25, 53.52, 57.40, 125.73, 126.45, 127.78, 128.97, 128.76, 128.88,
129.26, 132.76, 136.35, 139.14, 140.57, 141.32, 145.41, 173.91, 207.63; HRMS (CI+) m/z calcd
for C30H31NO5S [M]+; 517.1923, found 517.1914.

(±)-Methyl(3S,4R,4aR,13bS)-3-hydroxy-4,13b-dimethyl-2,3,4,4a,5,6,8,13b-octahydro-1H-naphtho[2,1-b]carbazole-4-carboxylate (233)

NH

HO
MeO2C

H

234

233 (381 mg, 1.05 mmol)

1,4-/(21 mL)$",/`(2.1 mL)

Pd(OAc)2 (70.7 mg, 0.315 mmol)dCu(OAc)2 (70.7 mg, 0.315 mmol)
3T^I 48 BaA@d10%S`,(]d_`-HJe K

Q\d=P

M3eWF<91d

L6,-#

N8RZd10%S`,(-.'+%0(&/fAcOEt = 4:1)Y[ 234

L6,
>(285 mg, 0.756

mmol, 72%). 234: pale yellow syrup; FT IR (neat) cm-1; 3525, 3408, 3295, 2951, 2875, 28752,
145

1700; 1H NMR (500 MHz in CDCl3) δ 1.17 (3H, s), 1.53 (3H, s), 1.55 (1H, m), 1.66 (1H, dt, J= 4.0 Hz, 13.5 Hz), 2.04 (2H, m), 2.25 (2H, m), 2.56 (1H, dt, J = 3.5 Hz, 13.5 Hz), 3.00 (1H, m),
3.11 (1H, dd, J = 3.5 Hz, 15.5 Hz), 3.22 (1H, dt, J = 4.5 Hz, 12.0 Hz), 3.55 (1H, d, J = 12.0 Hz),3.71 (3H, s), 7.03 (1H, s), 7.19 (1H, m), 7.35 (2H, m), 7.83 (NH, br s), 7.96 (1H, s), 7.99 (1H, d,
J = 8.0 Hz); 13C NMR (100 MHz, in CDCl3) δ 21.30, 23.61, 23.75, 29.27, 33.02, 38.22, 28.90,
49.03, 51.31, 52.81, 78.15, 109.64, 110.45, 117.02, 119.11, 119.91, 122.15, 123.38, 125.45,
133.56, 138.14, 139.39, 140.06, 178.60; HRMS (CI+) m/z calcd for C24H27NO3 [M]+; 377.1991,
found 377.1984.

(±)-Oridamycin A (74)

NH

HO
HO2C

H
(±)-74234 (52.0 mg, 0.137 mmol)(615 mg, 2.74 mmol)
4:

KEt2O

MgSO4 &5 DMSO(2.7 mL)<EK*;

8#L130 °C  24 1H0/

1.0 M )G"?

K23@

K!B

$
>L%.

J'I)567L

,K>K9(=CKF+(H2O/CH3CN =10:1)AD 74-(40.8 mg, 0.112 mmol, 82%). 74: white syrup; FT IR (neat) cm-1;

3525, 3408, 3295, 2951, 2875, 2852, 1700; 1H NMR (500 MHz in CD3OD) δ 1.28 (1H, s), 1.50
(3H, s), 1.52 (1H, m), 1.61 (1H, dt, J = 3.5 Hz, 13.5 Hz), 1.93 (1H, m), 2.13 (1H, m), 2.24 (1H,
dd, J = 6.0 Hz, 13.5 Hz), 2.32 (1H, dq, J = 4.0 Hz, 12.5 Hz), 2.60 (1H, d, J = 13.5 Hz), 2.98
(1H, ddd, J = 6.0 Hz, 13.5 Hz, 16.5 Hz), 3.09 (1H, dd, J = 4.0 Hz, 16.5 Hz), 3.25 (1H, dd, J =4.5 Hz, 12.0 Hz), 7.09 (1H, d, J = 7.5 Hz), 7.28 (1H, dt, J = 1.0 Hz, 7.5 Hz), 7.34 (1H, d, J =8.0 Hz), 7.96 (1H, s), 7.96 (1H, d, J = 8.0 Hz); 13C NMR (125 MHz, in CD3OD) δ 22.42, 24.51,
24.69, 30.22, 33.96, 29.53, 39.93, 40.30, 49.72, 54.02, 79.01, 110.57, 111.32, 117.42, 119.24,
146

120.48, 125.97, 134.41, 140.02, 140.29, 141.96, 181.03; HRMS (CI+) m/z calcd for C23H25NO3[M]+; 363.1834, found 377.1835.

Fig. S2 13C-NMR +;(±)-Methyl(1R,2S,3S,4aS,10aR)-3-bromo-2-hydroxy-1,4a-dimethyl-7-(N-phenylphenylsulfo
namido)-1,2,3,4,4a,9,10,10a-octahydrophenanthrene-1-carboxylate (235)

NBs
Br
HO
MeO2C

H

235

224 (33.3 mg, 0.0643 mmol)

8=6!(0.96 mL)1:?0 °C  TMSBr (25.5

μL, 0.193 mmol) .

@ 4<, 2 )>('?/$27@ "&*

0



10%3=



2:1)59 235-#



(AAcOEt =%. 235: pale yellow syrup; FT IR (neat) cm-1; 3502, 3064, 2950,
147

2870, 1722; 1H NMR (400 MHz in CDCl3) δ 1.31 (3H, s), 1.37 (3H, s), 1.57 (1H, m), 1.74 (1H,
dd, J = 2.0 Hz, 12.8 Hz), 2.07 (4H, m), 2.77 (4H, m), 3.74 (3H, s), 4.29 (1H, dt, J = 8.8 Hz,
12.0 Hz), 4.91 (1H, d, J = 12.0 Hz), 6.92 (1H, d, J = 2.4 Hz), 6.98 (1H, dd, J = 2.4 Hz, 8.8 Hz),7.06 (1H, d, J = 8.8 Hz), 7.27 (7H, m), 7.59 (1H, tt, J = 1.2 Hz, 6.8 Hz), 7.79 (1H, dt, J = 1.2
Hz. 6.8 Hz); 13C NMR (100 MHz, in CDCl3) δ 19.46, 21.01, 30.17, 30.65, 39.01, 48.29, 48.97,
50.54, 53.07, 54.71, 72.29, 125.99, 127.37, 127.74, 128.36, 128.51, 128.85, 129.21, 132.73,
134.93, 138.80, 140.54, 141.31, 147.92, 175.22; HRMS (CI+) m/z calcd for C24H28O3 [M]+;675.0290, found 675.0298.

(±)-Methyl(1R,2R,4aS,10aR)-2-hydroxy-1,4a-dimethyl-7-(N-phenylphenylsulfonamido)-1,2,3,4,4a,9,10,10a-octahydrophenanthrene-1-carboxylate (236)

NBs

HO
MeO2C

H

236

224 (333 mg, 0.643 mmol)ING,''(9.6 mL)@LP0 °C  TMSBr (255 μL,

1.93 mmol) <+Q+CM: 2 7O65# (1.04 mL, 3.56 mmol) AIBN(21.1 mg, 0.129 mmol)

 15 *O65
.48>

P1?

PJE9(15 μL)

10%BN$"

AcOEt = 2:1)FK 236<+Q

)-$%<+Q+CM:

2P.4;/D=0AHP;/$%&!#(('R

3(301 mg, 0.589 mmol, 90%). 236; white syrup; FT IR(neat) cm-1; 3457, 3064, 3028, 2952, 2930, 2875, 2839, 1710; 1H NMR (500 MHz in CDCl3)
δ 0.99 (3H, s), 1.35 (3H, s), 1.37 (1H, d, J = 4.5 Hz), 1.74 (2H, m), 1.93-2.04 (4H, m), 2.30 (1H,m), 2.78 (2H, m), 3.66 (3H, s), 4.19 (1H, s), 6.92 (1H, d, J = 2.5 Hz), 6.97 (1H, dd, J = 2.5 Hz,
8.5 Hz), 7.16 (1H, d, J = 8.5 Hz), 7.26 (5H, m), 7.48 (2H, dt, J = 1.0, Hz, 7.5 Hz), 7.59 (1H, dt,
J = 1.0 Hz, 7.5 Hz), 7.71 (2H, m); 13C NMR (125 MHz, in CDCl3) δ 13.62, 17.52, 20.33, 20.35,
22.54, 22.56, 23.75, 27.06, 27.85, 31.75, 32.53, 38.07, 44.51, 47.70, 51.31, 70.46, 127.33,
148

127.77, 127.79, 128.25, 128.27, 128.82, 128.84, 129.17, 129.18, 132.68, 147.32, 177.43;
HRMS (CI+) m/z calcd for C30H33NO5S [M]+; 519.2079, found 519.2073.

(±)-Methyl(1R,2R,4aS,10aR)-2-hydroxy-1,4a-dimethyl-7-(phenylamino)-1,2,3,4,4a,9,10,10a-octahydrophenanthrene-1-carboxylate (237)

NH

HO
MeO2C

H

237

236 (236 mg, 0.454 mmol)

%"(9.1 mL109 mg, 4.54 mmol) <'L40 °C  3

3H21

@EL)06>

K?.

Et2O J+-($7?:<'45C

J+I-789L45C

MgSO4 &BK=,@EK

10%AG!

;*!"#DF 237%($MAcOEt = 2:1)

/(165 mg, 0.436 mmol, 96%). 237: colorless syrup; FT IR (neat) cm-1;

3526, 3389, 2956, 2927, 2880, 1714; 1H NMR (500 MHz in CDCl3) δ 1.03 (3H, s), 1.36 (4H,m), 1.76 (2H, m), 2.01 (4H, m), 2.32 (1H, m), 2.81 (2H, m), 3.67 (3H, s), 4.21 (1H, s), 5.58
(NH, s), 6.76 (1H, d, J = 2.5 Hz), 6.89 (2H, dt, J = 1.0 Hz, 8.5 Hz), 7.15 (1H, d, J = 8.5 Hz),7.24 (2H, m); 13C NMR (125 MHz, in CDCl3) δ20.64, 22.60, 23.79, 27.19, 32.05, 32.79, 37.76,
45.05, 47.79, 52.24, 51.27, 70.66, 116.45, 117.36, 117.91, 120.46, 126.46, 129.29, 136.49,
140.39, 141.05, 143.61, 177.57; HRMS (CI+) m/z calcd for C24H29NO5S [M]+; 379.2147,
found 379.2143.

(±)-Methyl(3R,4R,4aR,13bS)-3-hydroxy-4,13b-dimethyl-2,3,4,4a,5,6,8,13b-octahydro-1H-naphtho[2,1-b]carbazole-4-carboxylate (238)

149

NH

HO
MeO2C

H

238

 237 (150 mg, 0.395 mmol)

1,4-)(7.9 mL)&)T(0.79 mL)FPV

6E Pd(OAc)2 (26.6 mg, 0.119 mmol)VCu(OAc)2 (179 mg, 0.988 mmol)
54+V.IR? 48 ;U:9

V10%HT&$

QVST'>@W A

&'(#%!

C.WK<

B1&'

D3GNV10%HT&$*(")XAcOEt = 4:1)LO 238

B1

7(106 mg,

0.280 mmol, 71%)W238: pale yellow syrup; FT IR (neat) cm-1; 3516, 3410, 3295, 2930, 2875,
1714; 1H NMR (500 MHz in CDCl3) δ 1.14 (3H, s), 1.40 (3H, s), 1.84 (1H, m), 1.92 (1H, dd, J= 4.0 Hz, 14 Hz), 2.10 (3H, m), 2.28 (1H, m), 2.41 (1H, m), 3.06 (2H, m), 3.69 (3H, s), 4.25
(1H, s), 7.07 (1H, s), 7.18 (1H, m), 7.35 (2H, m), 7.87 (1H, br s), 7.96 (1H, s), 8.00 (1H, d, J =7.5 Hz); 13C NMR (125 MHz, in CDCl3) δ 20.86, 23.46, 23.85, 27.30, 32.84, 33.48, 38.42,
45.35, 47.84, 51.27, 70.64, 109.70, 110.42, 116.80, 119.87, 122.00, 123.47, 125.32, 133.99,
138.06, 139.86, 140.03, 177.69; MS (CI+) m/z 377 [M]+; HRMS (CI+) C24H27NO3 m/z calcd for377.1991, found 377.1996.

(±)-C3-epi-Oridamycin A (239)

NH

HO
HO2C

H
239

238 (26.0 mg, 0.069 mmol)(308 mg, 1.37 mmol)

2= DMSO (2.7 mL)FPV6E

C.W130 °C  24 ;U:9
150)/&$V-M,JW08

%*

6Et2O

1.0 M 3-

MgSO4 ,6)+062
10:1)/1 239

6#$.

54&'(7

!6

(H2O/CH3CN ="(20.8 mg, 0.055 mmol, 80%). 239: colorless syrup; FT IR (neat)cm-1; 3525, 3408, 3295, 2951, 2875, 2852, 1700; 1H NMR (500 MHz in CD3OD) δ 1.26 (3H, s),
1.38 (3H, s), 1.81 (1H, ddd, J = 3.0, 6.5 Hz, 13.5 Hz), 1.93 (1H, dt, J = 3.5 Hz, 13.5 Hz), 2.08
(1H, dd, J = 2.0 Hz, 12.0 Hz)62.15 (2H, m), 2.18 (1H, dt, J = 6.0 Hz, 13.5 Hz), 2.43 (1H, m),
3.10 (1H, m), 3.05 (2H, m), 4.13 (1H, t, J = 2.5 Hz), 7.07 (1H, s), 7.09 (1H, dd, J = 1.0 Hz, 8.0
Hz), 7.29 (1H, dt, J = 1.0 Hz, 7.0 Hz), 7.35 (1H, d, J = 8.0 Hz), 7.96 (2H, m); 13C NMR (125MHz, in CD3OD) δ 20.86, 23.086, 23.44, 26.96, 32.70, 33.57, 38.36, 45.50, 70.03, 109.25,
109.98, 116.05, 117.86, 119.11, 121.76, 123.22, 124.57, 133.39, 138.61, 139.45, 140.62,
180.01; HRMS (CI+) m/z calcd for C23H25NO3 [M]+; 363.1834, found 377.1835.

151

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