1,2 vs. "!  3

1,2-Za"< 1) 0;AC!<&/$F(X = COR, CO2R, CN, NO2, P(O)(OR)2, SOR, SO2R, BR2)2) %(;AC!<&/$F(X = OR, NR2)
3) &<);AC!<&/$F(X = SiR3, SR, SeR)
4) #.6@74JVTQHOF?8B7"
(X = halogen, OSO2R, OR)
2) %( (JVUGPIX<4) JVTQHO<Z1>2>3)

*,3F5E#. <';AC2A>/ <JVTQHO<Y31D+.JVTX=GVLX:(MKWSWRX)CHCl3:KOH9
CCl2JVTX3→GVLX:<9NKWWMKWSWRX

1,2%',G/J!ZkdbYaS

4p Zk d b Y a S!

!
Di_h→/J!ZkdbYaoAIZkdl/*!ZkdbYaS>pAIZkdlS^clE

!
Xk[keilS1;1(homologation)\`lS#B7(S0!Xk]nkLV[ik4:1;+9(Cb = CONiPr2)
ACIE 2011, 50, 3760.

>pYjaTZkdbYaQNP6OW
OO

S CH2 +O

+ Me2S O
95%&$SZkdl  8H ?
 3 ISBN 9784815806064',"  -2.CmC =?
)  ISBN 9784807907601

ZkdbYaS@<homologationRUWF M5KfjgnS"JACS 2003, 126, 12179.

1,2

0$M (/)AJCJIDBH;(! 90;

&;"9 @−78℃
PMDTA!8".
→AGK/83 : /; :/5=62lone pair@79(/)34?=62(#8;<4?>)

pp-s* ;+MAEFL(n-s*'%)1,* p116

a:b= 36:64 (H2O)

8 7  3 A ( R 7 )     ( N Q 5 ?      d X )k6Â¦wi§¤(1-29v ¡)
Hicks, J.; Vasko, P.; Goicoechea, J. M.; Aldridge, S.
Reversible, Room-Temperature C—C Bond Activation of Benzene by an Isolable Metal Complex.
J. Am. Chem. Soc. 2019, 141, 11000-11003.

k6¦iyG0°©³¼Ba¦ ' i,a\6KPDF}k6V}
4IHq½ºÁ³¦ª«·®©³Z~µ¯¿Á´3335
http://oec.chembio.nagoya-u.ac.jp/docs.html]:¤\6KBa¦i§^c_(c¡)¤k6; ¥¤-(À­»¶YoDo#[ÀM0Supporting Information J²Á°ÀP¯¹¬³¼bsÀ!Cp/fUÀz!J.¦Lb¤}=61J  ZÀk6  Z¦Og¥¢¡£}^£¤(R7l[bhÀeª«·®©³Àk6" u  ÃÀk6]:¡NQ¥ ÃÀk6 ¥r ÃÀ¥¡& ¡+¢¥  ÃR7l[)¢¥¢S¤¡À+¢¥W>¦h8¤$|\¢¥¤ ÃÀ^¢k6 ¦m¢E¨¸¾Á±¦\¤ Ã¨¸¾Á±%,a$¤ Ã¤¢¥k6;¤ÃFx6K@T,a~¥¢NQ5?¦`ta2{R7l[nl[<*½ºÁ³¦j(4IHq½ºÁ³ eª«·®©³Z)

£)

13

+' #'#&*%*+()$*

BN



ACIE 2009, 48, 973.
JACS 2011, 133, 11508.

BN !
"general review:
Can. J. Chem. 2009, 87, 8.

13

A903<46@

1=:<?A903<46@≡[B12H12]2−

1=:<?( [C2B10H12]8?5?(,)'[CB11H12]−

ortho[C2B10H12]

meta[C2B10H12]

'#$*!
BNCT = Boron Neutron Capture Therapy
10B + n → [11B] → 4He(a-ray) + 7Li

'#$*

2?'

.;>/7

para[C2B10H12]

%+&"*

13%G>25A67F)

4B?AE.G1;3E[CB11H12]−0(#1;3E,*+(1)tert-Bu483E.!

dC 334.2(SO2)

(2)Wheland&@9B

483E.'-
(3)4B?AE$(.$)3.530 Å3.489 ÅJACS 2005, 127, 7664.
JACS 2006, 128, 3160.

(4)<AFCEC60.=D:E
483E/" .
NMR,
C–CH3 = 1.429(4)–1.459(4) Å
ACIE 2004, 43, 2908.

JACS 1972, 94, 2034.
JACS 2003, 125, 1796.

Science 2000, 289, 101.

138
WYZ6\(*CVJ60

\WYZ6C

()

7

!
ML[XAC!

!

A

=?UYQZI(=6)KNPXC"\'C/1KNPXD4:KNPXBFG

9'A. I>GA,#
SRTOX5@'C&E/1
Nature 1995, 374, 345.

3 @+#$B-;%) @<HG 2

JACS 2008, 130, 11872.

Boronic Acids
Ed by Deniss G. Hall
Wiley-VCH, 2011

13

B 9 A ? =:@ / 

9A<A9A?=:@/
Al-Al/.'*0
"!65,&79A<A" #%61.-4.$

9A<=A0)/22
>;=A0'3( +8(513-]IXTRX 4SG#=!&'?*79: 7@85;C]EXQ\X]XFO+%1]Flustrated Lewis Pairs"/<AB2< 7;2XFO+:
XFO>= :; D8C

ACIE 2010, 49, 46.

Organic Syntheses, 1993, Coll. Vol. 8, 578.

]CBS(Corey-Bakshi-Shibata))

JACS 1987, 109, 5551.
TVZ(BH3)>,792C4HJLMTYWNZ>%,( -.D36:;5
FUZ[RPWX[ENWNZ@$0#[EXKZ
KPZD#8C

Ishihara, K.
Lewis Acids in Organic Synthesis
Yamamoto, H., Ed.
Wiley-VCH: Weinheim, 2000.

13,MI=B*'
MFriedel-Clafts<I?I.

!M>F?AE6-K*$6;(23+5 &FHGL*$"6FHGL 71:4/9

Makromol. Chem. 1969, 130, 210.

!M@DJ6%)#$

!M*$08 /3*>BCI6-+5 &FHGL

MAD: methylaluminiumbis(2,6-di-tert-butyl4-methylphenoxide)

Organometallics 2011, 30, 3217.
JACS 1988, 110, 2650.

13!
1/92+; 1 / 9 6 . 8 &1/92+



$

http://www.chem-station.com/odos/2009/06/brown-brown-hydroboration.html

1/92+*8,837:'



JACS, 1964, 86, 3565.

1/9*840+51/92+

cat = Rh(PPh3)3Cl
ACIEE 1985, 24, 878.
0.05 mol%, 20 min, 83%*8-08*840+5'

(Rh-B )%"

# # 1/92+

Can. J. Chem. 1973, 51, 2098.

13

LiDip N B N Dip
BrDip = 2,6-iPr2C6H3
H2O

HOMOTHFDip N B N Dip
LiDip N B N Dip
Li1) PhCHO
2) H2O

nBuCl

Dip N B N Dip Dip N B N Dip Dip N B N DipnBu
HC
Ph H OH
Science 2006, 314, 113. ACIE 2007, 46, 6710. JACS 2007, 129, 9570. ACIE 2008, 47, 6606. JACS 2008, 130, 16069. Chem. Lett. 2008, 37, 802. JACS 2009, 131, 14162. JACS 2010, 132, 11449.
Chem. Commun. 2011, 47, 5888. ACIE 2011, 50, 920. Eur. J. Org. Chem. 2011, 3951. ACIE 2014, 53, 6259. JACS 2016, 138, 3548. ACIE 2016, 55, 11426. ACIE 2016, 55, 12827. ACIE 2017, 56, 1658.


Cy3P·BH2ILDBBO

Cy3P·BH2–Li+ClSiMe3

Cy3P

–•

LDBB = Li+B
H2

SiMe3

Mn Mn

COCOOCOC

OC COMn B Mn

LiDME

OC

MeI

CO

Li+(DME)3OOMeB

LDBB = Li+PhPhCl

then, H2O

pinB
PhO

96%Ph2

ACIE 2010, 49, 9166.

OO

Tetrahedron Lett. 2000, 41, 6821.
Chem. Lett. 2000, 29, 982.
then, H2O
J. Organomet. Chem. 2001, 625, 47.
PhPh
PhPh
Ph
Ph
K
MeI
KC8PhPh
Ph
Ph
Ph
PhB
BB
Mes
Mes
Et2O
Et2O
MeClNN
Mes N
N Mes
Mes N
Mes N

B Cu•KCl

Mn Mn
DME OCCOCOOC2–•

CuOTf (10 mol%)nBu P (11 mol%)3O

CuCl, LiCl, KOAc

ACIE 2008, 47, 5650. ACIE 2009, 48, 9735.
OEt
EtOO
Dip N C N Dip LDBB/TMEDA Dip N C N Dip
Dip N C N Dip
THF
BH I
BH Li
BH2+OO(B2pin2)

J. Org. Chem. 1994, 59, 6753.
J. Organomet. Chem. 1993, 462, 107.

ClB

B B

O

EtpinB53%

ACIE 2010, 49, 2041.

8 4 %
84%#Dip
BrN
KC8C B
Br
Et2O
N
Br
Dip
Dip = 2,6-iPr2C6H3

Dip N
Dip N
C N
C N
H
H
Dip
Dip
H
B B
B B
+HDip
Dip
H
H
N C
N C
N Dip
N Dip

#
NN

84%# 0+ -(JACS 2007, 129, 12412. JACS 2008, 130, 3298.
Mes Mes
NNMg Mg
NN
Mes Mes
Et3P

DurBEt3PBr

Et3P Dur
Dur = 2,3,5,6-Me4C6H1Nat. Chem. 2013, 5, 115.
Dip
BrN
Dip Br
B C
NNC B
Br Dip
NBrDipDip = 2,6-iPr2C6H3



Li

B B

THF

N CN

84%# / λmax = 538 nm (ε 4100)
red color& - '2
ACIE 2012, 51, 9931.

.

+ Br Pt B

84%#B
ClCl

B=B 1.590(5) Å

B=B 1.560(18) Å(cf. B–B ca. 1.75 Å)

84%#C

N
C N

Et3P

ESRPtBB

DurDur

THF

Science 2012, 336, 1420.

Mes

79:.Dur-B=B-Dur ( )12B-B )*,3



Na

Et3P

Mes
B B

BAr4

Mes
PEt3
Ar = 3,5-(CF3)2C6H3

B=B 1.449(3) Ålmax = 600 nm

# 12$$576

Mes
B B84.")!

84%#Dip
Dip
NN
C B B C
N
N
Dip
Dip

Et3P

CN
Dip

B B

CN
Dip

PEt3

BAr4

ACIE 2014, 53, 5689.

.
H2

Dip N
CH
B B
HC
N Dip

+
Chem. Eur. J. 2016, 22, 17169.

7&eZ1-nfgik:*%!CH4

BH3HCHcarbeneH B
borylene

8"KRTBVEfgik
Me2N

NH3

H N
nitrene5L-RTQ
2A2)J>/M< !9 I4@SVG>UOC

Mn
CO

Dip
NC

KC8Dip
NCHB

Dip
Dip
H H
NNC B C

TfOHs

CAAC

KC8Br B CN
Br

CAAC =Dip
NCCN

B

CAAC

NCCN

CAAC

B

NC

B

CAAC

NC

Dip N CH H

NHCI+OG01AFJ>EPK
σabm!lπX\^c_m!A'CG,1IQ C?U[hdkLσ !Iπ!W.
eZ1Acj`kBVU
Science 2011, 333, 610.

hY]fgikHL3$

H2

Dip N C

TfO

B

ACIE 1995, 34, 825.

Cf. CAAC (cyclic alkyl(amino)carbene)

BBr3CAAC

SiMe2PhO
OCCMn MnC B COO
NMe28 N6CGCE(LhY]L6HBVEfgik
Dip N C

Cl
B B
NMe2
ClScience 2007, 316, 439.

 KfgikIhY]7!eZ1W#F
;!L
N

CAAC
NC

B

N
N

eZ1HhY]A3$ DU
ACIE 2016, 55, 14464.

Cl Ph
B
NNO

B
Ph Cl

KC8O

N

O C

PhB
B
Ph

N

C O

TfO Ph
B
NN

MeOTf
OO
B
Ph Me

LeZ1AhY]=AhY]7Nat. Commun. 2015, 6, 7340.

)F <!
K;A1 6 8 GJLN42H22)

DipN

B N(SiMe3)2Dip
N

H2(1 bar)
toluene
25 °C, 24 h85%

Dip
NHHB
N(SiMe3)2HB(I)42)9"
H N(SiMe3)2 DFT& 168$
BAngew. Chem. Int. Ed. 2014, 53, 13159.

@GIN2B-B#B

B

0H22HCB?A

H2(1 bar)hexaneRT, 2 h52%

B

H
H

S

B(II)-7B(III)42)
'/3B.K;A)/
B-B# + .H+9

B

J. Am. Chem. Soc. 2017, 139, 2593.

B
H

2Li+H2(1 bar)

THF-d8100 °C, 2 dquant.

H H
B

B B

S

H2(1 bar)
tolueneRT, 1/4 h73%

SBH
H

B

Chem. Lett. 2017, 46, 1714.

@GI:NDIBN@:E=N42H2
HBS%!42*CH3B

2Li+B
H HtBuNPhPhPhB
CH3(37 mol %)H2 (1 bar)

>MM?IN2(15,82Li+tBu

HN

H
Ph Ph
H H

H
H
PhAngew. Chem. Int. Ed. 2016, 55, 14067.
H H

J. Am. Chem. Soc. 2019, 141, 6082.

3   + L J KG I E H .= $<708(NH4)2[Ce(NO3)6]>
1-*:48 3
SmI2>1-(:48 3

EFK<708+="<708+,<708

JKGIEH=EFK>f-1-:;C>+1":;Cd-D6;0=9p%):! 4<30→'#+AB?20=9/)&D:B@50→

3, . 1 W !   5      |  ] o7M9:*+z%JACS 2001, 123, 2466.

1G+Mo@OChem. Rev. 2002, 102, 2187.

YRE.1II p199-

SoLa`tpLiqoVntu> U)&a86

DU)91,2-(Fohro^.1W!
IJ/'Z"/? A
RQ=|}{{  1992
ISBN 4061533444
YRE.1II p35-

J. Organomet. Chem. 1985, 285, C21.

RLilCeCl3x4evdlkRCeCl2aPKG~NHW!o [l7kfwgwo 3& oaevzoD/L45+~NHo
1H NMR(\)

MRIT$doqya
Lsebmij_v

1H0o;

Gdo#<&ntuuo2 o1H NMRn`cv
CB-XT1aev