Fukuyama Group - Group Meeting Problems 05/07/2008

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2
3
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I
Me
Me
Fukuyama Group - Group Meeting Problems
05/07/2008
N
H
MeO2C OBn
OBn
NH•HCl
TBS OH
+
O
OsO 4, NMO
BCl 3
O
Me
t BuOMe- t BuOH-H2O
94%
CHO
solvent
(CH 2Cl 2 or toluene?)
Cl
1) NBS, Me 2S, CH 2Cl 2
–20 ºC to rt
2) n-BuLi, CH 3CN
THF, –80 ºC
1) CH 2Cl 2, rt, 3 d; neutralize
2) THF, rt, 12 h, 69%
3) Et 3N, THF, reflux, 32%
(COCl) 2
DMSO, Et3N (PCy3) 2Cl2Ru=CHPh CH2Cl2, –78 ºC; CH2Cl2, reflux;
78%
MgBr
medium ring
intermediate
quant
(determined by GC)
R. Priefer et al., Tetrahedron Lett., 49, 2677 (2008)
I
N
H
N
H
Me
O O
CO 2Me
M. E. Kuehne et al., Tetrahedron, 39, 3707 (1983)
LTA
95%
M. Hirama et al., J. Am. Chem. Soc., 125, 10772 (2003)
3) mCPBA, CHCl 3
4) NaHMDS, THF
–30 to 5 ºC
LHMDS
THF
–100 ºC
85%
TBSO
Z
HO Me
CN
Me
OBn
OBn
K. Takeda et al., J. Org. Chem., 70, 10515 (2005)
H
O

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A =
Fukuyama Group - Group Meeting Problems
05/21/2008
Ph
PMBO
O
MeO
Ph
TMS
O
O
NHOH·HCl
OH
CO 2H
Me
Cr(CO) 5
O
Me
1)
NC
(1.2 equiv)
CHCl 3, 150 °C (microwave)
75%
2) LHMDS (1.2 equiv)
THF, –78 °C to rt;
concentration;
TFA-CH 2Cl 2, rt
75%
1)
malononitrile (3 eq)
Et 3N (1 eq)
toluene, reflux, 2 h
CH 2Cl 2
O
S. J. Danishefsky et al., J. Am. Chem. Soc., 130, 5446 (2008)
2) 35 °C, 64 h, Et 2O;
DDQ, CH 3CN
51%
MeO
N
HO
M. F. Semmelhack et al., J. Am. Chem. Soc., 104, 5850 (1982)
1) n-BuLi, THF, DMPU, –78 °C;
trimethyl 4-bromoorthobutyrate, –78 °C to rt
2) H 2, Lindlar cat., py., MeOH
3) A, toluene, MS 4A, 45 °C; Et 3N, 75°C
53% (3 steps)
4) Zn(BH 4) 2, Et 2O, –10 °C, 84%
O
Me
TMS Me
NC CN
NH2 S.-X. Liu et al., J. Org. Chem., 73, 3596 (2008)
OH
O
O
PMBO
O
O
Ph
Pr
O N
HO
C. Kouklovsky et al., Org. Biomol. Chem., 6, 1502 (2008)
Ph