Fukuyama Group - Group Meeting Problems
04/02/2008
1Me1) Br2
AcOH/H2O (1:1)
0 °C, 77%ON
HSO2Phtetracyclic
compound*1) L-selectride
THF, −78 °C;
PhNTf2, 70%

10% Na(Hg)Me
Na2HPO42) toluene (0.05 M)
2) HCO2H, Et3N
reflux, 70%
PdCl2(PPh3)2*except for Ph group DMF, 60 °C
84%

H
H
N

THF/t-BuOH(3:1)

H

82%

K. M. Peese and D. Y. Gin et al., Org. Lett., 7, 3323 (2005)21) PhI(OH)OTs (1.0 eq)
p-TsOH, MeOH
–72 to 30 °C, 2.5 h;
refrigerator
2 weeks, 55%1) vinylMgBr
THF, 89%O

C15H22OSi2) HMDS, I2
CH2Cl2, 99%
C10H10OOOOO2) cat. RuCl3, NaIO4
H2O-CCl4-MeCN (3:2:2)
1.5 h, rt, 83%

C24H24O4

L. F. Silva et al., Org. Lett., 10, 1017 (2008)

3
LDA (1.05 equiv)
Et2O, 0 °C;

OPhN
MeOtBuN
MePhMgCl (1.2 equiv)
ZnCl2 (1.2 equiv)
THF, –78 °C to rt

NaNO2 (xs)
CH2Cl2-Ac2O-AcOHrt;

O
Ph

filtration;
evaporation;
NaHCO3, MeOH
refluxNMeOMe
Ph74%, dr = 87:13
84%
P. Somfai et al., Angew. Chem. Int. Ed., 47, 1907 (2008)

4MeMeMeOTIPS

1) AuCl (1 mol%)
CH2Cl2, 88%Me2) HCl, MeCN
91%O

MeMeS. A. Kozmin et al., J. Am. Chem. Soc., 126, 11806 (2004)

Fukuyama Group - Group Meeting Problems
04/09/2008
1OH

1) HC(OMe)3mesitylene
220 ºC, 70%1) ethyl vinyl ketone*
DAIB*, MeOH, 98%

OMe

C17H28O4Si

2) TMSOTf*, Et3N*benzene, 99%

Me2) 1% (CO2H)2
Et2O, 95%

MeOOOMeOMeMeC.-C. Liao et al., J. Org. Chem., 73, 2554 (2008)*theoretically 1 eq.

2MeOO

MeL-Selectride
THF, -78 °C;

1) Pd(PPh3)4, LiCl, CO
Bu3SnH, THF, 70 °C

PhNTf2, 82%2) PhTsN

OBn

Ph –78 °C to rt

71%
B

NTs

KH, 18-C-6
THF;
Me2SO40 °C, 98%

MeOBn

A. B. Smith. Ⅲet al., J. Am Chem. Soc, 129, 14873 (2007)

3(–)-sparteine (1.2 eq)
s-BuLi (1.2 eq)
Et2O, –78 °C;

Boc
NMeBocHN
OH

BEt3 (1.4 eq), –78 °C;
TMSOTf (1.0 eq)–78 °C to rt;
NaOH, H2O2, H2O0 °C to rt
58%, 90% ee

V. K. Aggarwal et al., Org. Lett., 10, 141 (2008)

4MeTMSOON31) TiCl4,CH2Cl2–78 to 0 °C, 68%3) O3
CH2Cl2, –78 °C;
Me2S, 96%2) PCC, NaOAc
silica, CH2Cl285%4) t-BuOK
t-BuOH, 40 °C
80%O
MeN
O

Y.-Q. Tu et al., Org. Lett., 10, 1763 (2008)

Fukuyama Group - Group Meeting Problems
04/16/2008
1O

CO2Et+Ph

SiMe3

N2THF
–78 °C;OILDA (1 eq) IOPh0 °COEt

84%
K. A. Scheidt et al. Chem. Commun., 1926 (2008)21) cyclopentadiene, Et3N
TFE/Et2O (1:1)−78 °C to rt

OBrBr

tricycliccompound

2) NaBH4, EtOH
64% (2 steps)

3) KH, THF, 0 °C to rt;vinyllithium−78 °C to rt, 67%O

H4) DMP, CH2Cl2, 0°C
H76%5) Grubb's cataylst
ethylene, CH2Cl275%
M. Harmata et. al., Org. Lett., 7, 2563 (2005)31)

NH2NClMeOOOMe

AcOHreflux, 2 h92%(COCl)2DMSO
CH2Cl2;2) ethyleneglycol
KOH, DMSO
50 °C, 94%

Et3N–78 °C84%

1H-NMR:1H
δ = 9.75 ppm

cat. TFA
PhNH2MeCN
reflux, 4 hNNOHN
Ph90%
X. Bai, Q. Dang et al., J. Org. Chem., 73, 3281 (2008)41) Et3N, DMAP, DCC
Meldrum's acidCH2Cl2; concentration;
NHTs
MeOH, reflux, 72%N
Boc

CO2H 2) Et3N, p-ABSA
CH3CN, 86%3) CuOTf, CH2Cl2
50%4) LiCl, H2O
DMSO, 130 °C
87%ONBoc NTsY. Qin et al., Angew. Chem. Int. Ed., 47, 3618 (2008)

Fukuyama Group - Group Meeting Problems
04/23/2008
1NH

1) PhC(O)CO2Et
neat, 90 °C

3) t-BuOK
toluene, reflux, 60 %2) TsNHNH2, HCl (gas)DME, reflux
80 % (2 steps)4) HCl (gas)
MeOH, 0 °C, 100 %N
H H
Ph·HClCO2Me

RitalinJ. D. Winkler et al. J. Org. Chem., 63, 9628 (1998)

2OH

O
NaOCN

SOCl2, Py

TFA-Et2O

toluene
0 °C to rt

PhMgBr

THF, –60 °C MeOH, 60 °C

88%

RHN

OROH

79% (2 steps)

85%

R=n-C13H27P(OMe)3S. M. Weinreb et al. J. Am. Chem. Soc., 105, 4499 (1983)

3PhO

O

O2N

(1 eq)MAPh

L-Selectride(1 eq)

CH3NO2/CH2Cl2–6 °C

CH2Cl2–78 °C

THF–78 °C

69%

94%

91%

OK(1 eq)Cl
Oi-PrOPhPh

H2 (160psi)
Raney Ni
C28H33NO7

ON

HO

MeOH
64%

HO

HO
C8H11NO4

PhO

O

Al
Me
Ph Ph

MAPh =(used as Lewis acid)

S. E. Denmark et al., J. Am. Chem. Soc., 118, 8266 (1996)

4HON
CO2Bn

OTHP

xylenereflux84%

bicycliccompound2) p-TsOH
MeOH, rt93%1) Ph3P=CHCO2Me
CH2Cl2, rt93%

3) (COCl)2
DMSO, CH2Cl2;
Et3N, –78 °C
97%2) Zn
AcOH-H2O, 50 °C
94%3) 1,2-dichlorobenzene
reflux
84%

MeO2C
HO HN
MeH

Z. Zhao et al., Org. Lett., 1, 681 (1999)