Fukuyama Group - Group Meeting Problems

07/02/2003

1) n-BuLi (1 eq); ClCH2SCl

1 OH
Et2O, –78 °C to 25 °C
A
2) mCPBA (1 eq), CH2Cl2
25 °C, 47% (2 steps)

1) A, 60 °C 1) A, 60 °C

2) t-BuOK 2) t-BuOK
THF, 0 °C THF, 0 °C
57% (2 steps) 85% (2 steps)

2 OMOM
LiN O (2 eq)
Li O
HO
Br –78 °C, THF; –78 °C, THF;
Br A
Br isobutylaldehyde, reflux aq. HCl, ethanol, 0 °C Br

73% 75%

3 OH
O
MeO Me
TsOH O
O
acetone, reflux
HO
n-Bu 82% n-Bu

4
1) PhCH2N3
MeO OTES BF3·OEt2 O
47%
N
2) Rh2(OAc)4 Ph
90%

5 SiEt3
SiEt3
H O H
HO
a) t-BuLi, Et2O-pentane c) Li O I O
I –78 °C, 30 min; 0 °C, 1 h
–78 °C

b) Pr-C CCu, –78 °C to rt d) I2

 Fukuyama Group - Group Meeting Problems
07/16/2003

1 t-Bu
1) lithium dispersion HO
Si
TIPSO Me t-Bu2SiCl2, THF t-Bu
0 °C to rt OHC

TIPSO Me
2) O2N

NC
CH2Cl2, rt;
aq. HCl/THF 56% (2steps)

2 1) NaH; BuLi;
I 3) hv (Pyrex) H
O acetone/MeCN CO2Me
CO2t-Bu 87% 0 °C
O
2) TFAA (2 eq) 4) p-TsOH (0.1 eq)
TFA (25 eq) MeOH, reflux H
acetone, 25 °C 80% in 2steps
59%

3
N C N S Ph
HO O PhH, reflux;
O

Ph S Ph Ph

4 NaH, THF; 1) BnNH2

toluene, reflux*;
EtSCH2COCl Bn Me
TMS OMs
O NaI, : 73% TsOH N
CO2Me O Me
rt to reflux 2) NaIO4 benzene
MeOH-H2O, rt reflux CO2Me
87% EtS
90%
61%
*Dean-Stark trap
5
LDA; t-Bu CHO m-CPBA
A
TMS THF, 61% CHCl3, 77%
N

380 °C
A N
N
10 sec, 60% t-Bu
O t-Bu
O
1.7 : 1
 Fukuyama Group - Group Meeting Problems
07/30/2003

1 1) TiCl4;
OSiMe3

SiMe3 OPh Me3Si OH

O Me 2) TsOH Me
BnO
OSiPh3 CH2Cl2, –78 °C benzene, 40 °C BnO
80% (2 steps) O O

2 1) PhOPh
Cbz reflux, 60 min
N CO2Me 90% MeO2C

2) SeO2 (2 eq) N
HCO2H (2 eq) Cbz OH
dioxane, 90 ºC
4 hr, 68%

3
MsCl
, BF3•Et2O Et3N DBU
OH H O O
CH2Cl2 CH2Cl2 benzene
N –78 ºC, 2 h rt, 2 h 80 ºC, 70 h O
O PMP NHPMP
85% 74% 61 %
racemic

4
O O
1) acetylene, hn

2) p-TsOH, benzene
reflux

N 1) Rh2(OAc)4 (1 mol%) Me
N Ph
130 °C
O Me Ph
Ph
2) Me2AlCl HO Me
Me Me