Fukuyama Group - Group Meeting Problems

10/01/2003

1
1) n-BuLi (theoretically 1 eq)
OMEM THF, –78 °C; Bu3SnCl O
–78 °C to rt, 59% A BF3·OEt2
Ph
SO2Ph 2) benzoyl chloride, toluene Dihydrofuran CH2Cl2
O
reflux, 83% –78 °C to rt
racemic 45%

2
1) LDA (1 eq), THF; MeI
–78 °C to 0 °C, 95%
2) toluene, reflux
S N
3) LDA (1 eq), THF; Br
S (all trans)
–78 to 0 °C, 90%
4) MeI, LiF, Li2CO3
DMF, rt (in the dark), 80%

MeO O O 1) TsOH•H2O
MeOH-H2O 3) K2CO3, MeOH MeO2C
reflux, 70% reflux, 88% N
C13H19NO3 H
2) toluene, reflux 4) SmI2, THF HO H
N 64% rt, 64%
O HO
O O

4
O Et
S Ac2O, DMAD OH
cat. TsOH CO2Me

O xylene, reflux
CO2Me
NEt2 NEt2

5
R
R
I cat. Pd(0)
+ R R + PhB(OH)2
Ph
 Fukuyama Group - Group Meeting Problems
10/08/2003

1 F F Zn, TMSCl F F
O MeCN, 100 °C, 20 h OH
Cl
; wet SiO2
O O
78%

2
O
N3 BF3•OEt2 N O
CH2Cl2
rt, 2 min
92%

MgX KHMDS KHMDS

O
THF toluene, 50 °C diglyme, 100 °C
Ph
O Ph
79% 67%

1) pyridine, benzene 2) PhMgBr, THF NHTs

rt, 1 h; –60 °C, 1.5 h
Ts-N=S=O
3) (MeO)3P, MeOH
reflux, 30 min NHTs
rt, 15 h 83% (2 steps)
43%

OMe OMe O
1) OMe MeO
O2 N Me 2) hν OMe
Li

80% MeOH Me N
OHC OMe
45% OMe
OMe HO
 Fukuyama Group - Group Meeting Problems
10/15/2003

1
1) PPh3;
N
O Ph
Me O Ph
Me 2) NaBH4
Me
Ph N
benzene glyme H
Ph Ph 85% 70% Ph Me

2 S 1) NaBH4, EtOH;
MeI, Na2CO3 S
S hυ, Pyrex rt, 69%
O A S
S benzene 2) MeI, Na2CO3
76% EtOH, reflux S
S 72%

3
Bn N Ph
n-BuLi; PhCN
N N
N THF toluene
N –78 °C to rt reflux Ph

4
MeS O
N + n-BuLi
O n-BuSH S
TsOH
OH
benzene THF
reflux –70 °C;
Dean-Stark Silica gel, 4 N HCl

5
MeO O
1) PhLi 2) TsOH, H2O OH
O (workup H3O+)
Me Me
 Fukuyama Group - Group Meeting Problems
10/29/2003

1
O
3) NaOH, H2O2
1) TMSCN, ZnI2 (cat.) n-Bu4NHSO4 O

2) POCl3, pyridine 4) 3N HCl

reflux

2
1) hυ (350nm) Me CO2Me
N PhCOCH3/acetone H

2) Me2CuLi O
O N
MeO2C

3
Ph Ph
1) xs. TFAA, xs. Py
CH2Cl2, 0 °C, 85% CN
2) Me3Al, NH4Cl
N PhH, rt; t-BuOK, 94% N
O Me Me

4
O H
N
O Ph
N
benzene, 406 °C Ph +
Ph
N O
14% 13%

5
S
1) S2Cl2, Et3N, Et2O (98%)
OH S O
2) CHCl3, reflux (69%)
O