Fukuyama Group - Group Meeting Problems

06/04/2003

1 OMe
1) decalin, 215 °C, 1h TsNH-NH2
A O
2) HCl, EtOH, rt AcOH, CH2Cl2
CO2t-Bu 3) NaOH, H2O2, H2O/MeOH 72% CO2t-Bu
68% (3 steps)

O O
P(OMe)2
2 OTBS 1) N2 , K2CO3, MeOH, 88%
A
CHO 2) TBAF, THF
3) Swern oxdn., 76% (in 2 steps)

H O
t-BuLi,THF, –78 °C; cat. MeLi

CeCl3 (anhydrous); Ph2O, 185 °C H

Br A
76%
82%
3
Ts
Ph N
Ts
Ar
20 mol% PBu3 Ph N Ar
• CO2Et CH2Cl2, rt
CO2Et
Ar = 4-CN-C6H4
99% (dr 98:2)

4
2) Ph S
2
1) t-BuO2C CO2t-Bu
O Br t-BuOK
t-BuOK DMSO, rt; 3) NaOMe MeO2C
CO2Me
t-BuOH, rt LiBF4 MeOH MeO2C
benzene, rt reflux
82% 74%

5
n-BuLi (2 eq), THF, –40 °C;
O
Ph
Ph N cat. Hg(OCOCF3)2
MOMO
t-Bu Me O TFA
Me t-Bu
OTBS –78 to –40 °C; CH2Cl2 O
aq. KH2PO4 rt, 36 h O

74% 71%
 Fukuyama Group - Group Meeting Problems
06/11/2003

1 OH O NH2NHCOOEt;
SOCl2 K2CO3, BzCl
C8H6N2OS SBz
–78 °C to reflux acetone, reflux O

92% 91%

2 H
N
CO2Et
N O t-BuOK, DMF; N
MeHN CO2H (EtO)2P(O)Cl;
O
F F NMe
DMSO CN CO2Et
O 100 °C t-BuOK O

3 1) N2CHCO2Et
BF3•OEt2
O 2) NH2OH•HCl
AcONa, MeOH
OPiv OPiv
3) NaNO2, FeSO4
AcOH-H2O

MeO O 1) toluene
TMS 110 ºC, 70% 3) TFA O
•
MeO
2) Ag2O CH2Cl2
MeO OH OMe K2CO3 90% (2 steps)
benzene MeO OMe
OH

5
Pd (PPh3)4 O
H
• CO
OAc O
AcOH, 75 °C
22% H

racemic
 Fukuyama Group - Group Meeting Problems
06/18/2003

1
O
Pb(OAc)4

OH N NH2 THF
N
74%
NHCOPh Ph

2
MeO2C CO2Me
1) NBS, CCl4 (hn) DMAD
BnSiMe3 A N
2) MeNH2, MeOH toluene, reflux Ph N
83% Me
3) NaNO2, H+

3
OH
N
cat. p-nitrobenzonitrile, KOH CN
H
DMSO, rt, 5 hr, 79%
O2N HO

4
1) (PhMe2Si)2CuLi2I; Ac2O
2) O OH OH
CHO
CO2Et , SnCl
4
PhMe2Si Me Me
3) LAH; I2, PPh3, 78%
4) Zn, AcOH, 82%

5
1) SeO2, TBHP, CH2Cl2 O
OH 2) AllylBr, NaH, THF O
3) DBU (2 eq), toluene, 220 °C
4) TPAP, NMO, MS4A, CH2Cl2
dr > 98%