Fukuyama Group - Group Meeting Problems

02/13/2002

1 O
Me PhSH PhSCl, Et3N; Me SPh
C11H12O2S
O2 H2O, 75%
O
major product

2 NO2
(EtO)2P NO2
Ot-Bu Ot-Bu H
1) mCPBA O

2) Al2O3 NaOMe, DMF, 0 °C

74%

3
Me MgBr
O OH
–70 °C;
Cl LAH, 10 °C

THF

4
OEt 1) Me2NH
ether
(OC)5W
Ph OEt
2) pyridine
PhC CCO2Et EtO2C NMe2
toluene
60 °C, 2 h

5 OH
OPiv 1) hv
acetone, rt

2) aq NaOH, EtOH O
O OPiv 3) Li, NH3
H
 Fukuyama Group - Group Meeting Problems
02/20/2002

1
PPh3CH3+I– (2 eq) H
t-BuOK (2 eq) (CH2O)n
HO
Cl
O sulfolane
H toluene
reflux 100 °C
84% 82%

2
1) n-BuLi (2.0 eq), TMEDA;
TMSCl, THF, 73% Ph
Ph SH Ph
2) O benzene, 180 °C OSiMe
93%
Ph Cl , Et3N
Et2O, 95%

3
Me Me
EtO EtO
1) MeOTf 3) MeOTf, CH2Cl2
CHO 4) TBAF, THF N N
N 2) TMSCH2NH2
45 °C H
CH2Cl2, 0 °C Me Me
Me
77% (2 steps) 70% (2 steps)

4
1) CH3C(OEt)3
O OH
O OH cat. prpionic acid
reflux OBn
OBn N
N Ph
Ph 2) NBS, DME-H2O CO2Et
Boc
3) EtONa, EtOH CO2Et
4) LiHMDS, THF, –50 °C

5
O 1) n-BuLi (2 eq), THF O
–78 °C to 25 °C
R n-Bu
O 2) Me(MeO)C=CH2, TsOH
MgSO4, CH2Cl2 O R
3) SnCl4, CH2Cl2
–78 °C to 25 °C
 Fukuyama Group - Group Meeting Problems
02/27/2002

1 1) HOBr
2) LTA, I2, CaCO3 HO
HO
hυ, cyclohexane Tl(NO3)3•3H2O

3) Zn, AcOH-H2O dioxane

R
HO
2
H
HO Swern oxidn
–78 to 0 °C;
NH3 (gas)
0 °C to rt; HN R

NH4OAc
AcOH;
rt to 70 °C
R = CH2CH2CH2OBn 82-95% overall yield

3
CO2Me MeO2C
PPh2Cl, Et3N
CH2Cl2, –78 to 0 °C;

xs.1,4-cyclohexadiene Me
PhH, 40 °C, 2 hr
PPh2
OH O
68%

4
1. Me3MgLi (1.0 eq) 1. n-BuLi, THF, 0 °C;
PhMe2Si SiMe2Ph THF, –78 °C n-C8H17I, rt C5H11 C8H17
A
Br Br 2. DBU 2. HBF4•OEt2, CHCl3, reflux; O
DMF, 90 °C TBAF, KHCO3, H2O2 aq 68% from A
THF-MeOH

5
Ph3P Ph xs. NO2, CH2Cl2 O2N NO2

O Ph rt
NC