Fukuyama Group - Group Meeting Problems 08/03/2005

1
2
3
4
5
Cl
O
HO
O
Me
Fukuyama Group - Group Meeting Problems
08/03/2005
O
HO 2C
N 3
Hex
1) CH 2N 2
Et 2O, 0 ºC
2) BF 3• Et 2O
Cl(CH 2) 3CN
0 ºC to rt
59% (2 steps)
3) cat. PdCl 2, CO
NaOAc, CuCl 2
MeOH, 67%
O
O
1) hν
acetone
75%
2) DPPA, Et 3N
dioxane, Δ
89%
CO 2Et
, Bu 3P
toluene, rt;
EtSCH 2COCl, Δ
44%
1) ClPh 2SiSiMe 2Ph
Et 3N, DMAP
2) t-OcNC (8 mol%)
Pd(acac) 2 (2 mol%)
toluene;
n-BuLi, THF
86%
1) (n-Bu 3Sn) 2
n-BuLi; MeI
THF, –78 °C
2) NH 2OH•HCl
NaOAc
MeOH, rt
3) RuO 2, NaIO 4
CCl 4, H 2O, MeCN;
2M aq.H 2SO 4;
55% H
O
C 13H 16ClNO 3
NaIO 4
NaHCO 3
H 2O-MeOH, rt
95%
3) c-HexCHO
TiCl 4
76%
J. K. Cowell et al., Tetrahedron Lett., 37, 2177(1996)
3) LTA (1 eq)
CH 2Cl 2
–60 °C to rt
4) LAH, Et 2O, rt
O
H
H
O
4) NaI
MeCN, reflux
5) PhSiH 3, CsF
MeCN, reflux
6) DDQ
48% (3 steps)
E. Vedejs et al., J. Org. Chem., 58, 1341 (1993)
NH 2
OH
Me
H
H. Nishiyama et al., J. Am. Chem. Soc. 107, 5310 (1985)
TFAA, CH 2Cl 2
0 °C, 10 min;
TFA, rt, 2 h
76%
H
A. Padwa et al., Org. Lett. 7, 1339 (2005)
c-Hex
OH
O
Me
N
Hex
Y. Ito et al., J. Org. Chem., 61, 4884 (1996)
O
O
SEt
CO 2Et
N
CO 2Me

1
2
3
4
MeO
5
O 2N
HO 2C
Fukuyama Group - Group Meeting Problems
08/10/2005
N
Bn
Ph Ph
Si
O
MeO 2C
O
N
H
Et
S
O NBoc
NH 2
NH
Br
O O
1)
Cl Cl
Zn
–78 °C to rt, 5 h
2) toluene, reflux
3 h, 66%
1)
Me2N OTBS,
MeCN;
HF·pyr, 25 °C
2) tol, reflux
60% (2 steps)
(CO) 5Cr
OMe
Me
hν (visible light)
ZnCl 2, CO (5 atm)
THF, rt
, 1
71%
>40%
>50%
O
, 1
NC
CHO
1) Pd/C, H 2 (4 atm), 15 h
2) LAH, THF
0 °C to reflux, 20 h
3) AcOH, 2 h
1) TFA, CH 2Cl 2
2) KOTMS, Et 2O
3) Pb(OAc) 4, DMF
0 °C
58% (3 steps)
I 2
MeCN, rt
69%
OMe
A. Padwa et al., Org. Lett., 7, 2925(2005)
H I
N
O
O
H
OMe
Me
Hegedus, L. S. et al., J. Org. Chem., 61, 2871 (1996)
Ph 2
Si
O
Ph 2
Si O
OMe
2. 2 eq. KHMDS
2 eq.
Br
N
H
N
H
D. Lee et al., J. Am. Chem. Soc., 127, 9410 (2005)
1. MeOH/THF, 48h, 67%
3. cat. 1, (see problem 4)
CH 2Cl 2, 69%
Et
A. Padwa et al., J. Org. Chem., ASAP
Mes
Cl
Ru
Cl
S. Screiber et al., Org. Lett., 2, 709 (2000)
N
N N Mes
PCy 3
1
Ph
Grubbs 2nd
Bn
N
O
H
N
O
O
H
O
H
H
N
Br