Fukuyama Group - Group Meeting Problems 06/06/2006

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Fukuyama Group - Group Meeting Problems
06/06/2006
PhS
OTMS
I CF 3 OCO 2Me
H 2N
H
OH
SiMe 2Ph
OPh
1) Br
O
i-Pr2NEt, MeCN
80%
2) mCPBA, Na 2HPO 4
CH 2Cl 2, –78 °C
84%
OBn
OBn
HN DBS
+
DBS =
1) Br 2, CH 2Cl 2
–78 °C, 95%
2) NaOH, EtOH
0 °C, 91%
BuLi;
A, cat. Pd(PPh 3) 4
85%
toluene
200 °C
(sealed tube)
78%
MeO B
O
O
[RhCl(C 2H 4) 2] 2 (3mol%)
dppf (6mol%)
Et 3N, H 2O
dioxane, 100ºC
CHO
I
OBn
OMe
81%
O
CO 2Me
HCl
Et 2O, rt
91%
tricyclic
compound
1) ZnI 2, EtOH
60 °C, 82%
A
C9H9BrS O
T. Cohen et al., Org. Lett. 8, 2087 (2006)
Y. Lisag et al., J. Org. Chem. 70, 6980 (2005)
1) DIBAL
CH 2Cl 2, –78 °C
87%
2) PMBNH 2
H 2, Pd/C, EtOAc;
(p-NO 2C 6H 4O) 2CO
81%
HO
Me
N
OH
O
N
PMB
R. M. Williams et al., Angew. Chem. Int. Ed. 43, 2930 (2004)
i-Pr
N N
i-Pr
i-Pr
i-Pr
(10mol%)
Ni(cod) 2 (5mol%)
toluene, 70ºC
90%
K 2CO 3
Pd(PPh 3) 4
DMF,100 ºC
73%
OBn
OBn
M. Murakami et al., J. Am. Chem. Soc. 128, 2516 (2006)
2) Pd(OCOCF 3) 2(PPh 3) 2 (10 mol%)
PMP, toluene, 120 °C
60%
F 3C
PMP = 1,2,2,6,6-pentamethylpiperidine
DBS
N
OMe
OBn
L. E. Overman et al., J. Am. Chem. Soc. 115, 11028 (1993)
O
CO 2Me

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Fukuyama Group - Group Meeting Problems
06/14/2006
O
EtO CN
n-Bu
Br
O
O
O
N
Hg(NO3) 2,
N
CH2Cl2 H
–40 ºC to rt, 2 h;
NaBH 4, MeOH
39%
CN
1. Zn, AcOH
100 ºC
65%
2. DAIB
KOH, MeOH
76%
1. Eu(FOD) 3 (10 mol%), 80 °C
2. hν
HCl
reflux
53%
C 14H 20O
NH
H
N
H. Heathcock et al., J. Org. Chem., 58, 564 (1993)
O
O
HO
MeO
N
OMe
W. Z. Li et al., Org. Lett., 5, 2931 (2003)
3. LiDBB, THF
4. PDC
• Ph Pr Pr
Ni(cod) 2 (10 mol%)
PMe 2Ph (20 mol%)
toluene, 50 °C, 5 h
O
Br
OEt
77%
C 15H 17NO 2
t-BuLi (4 eq)
THF
–78 to 0 °C
Ph
A
32% overall yield
Ni(cod) 2 (10 mol%)
P(4-CF 3-C 6H 4) 3 (20 mol%)
CH 3CN, 80 °C, 8 h
81%
Me
EtO
Me
O
O
Me
Pr
H
Me
CN
Ph
T. Hiyama et al., J. Am. Chem. Soc., 128, 7420 (2006)
O
O
OEt
–78 °C;
3% HCl-EtOH
reflux
89%
Rawal, V. H., et al., Org. Lett., 2, 2711 (2000)
O
Ph
n-Bu
Shindo, M. et al., J. Am. Chem. Soc., 121, 6507 (1999)
Pr

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Fukuyama Group - Group Meeting Problems
06/28/2006
+
O
O
Cy
O
OH
TMS
TMS
O
NH 2
O
O
S +
O- S
Cr(CO) 6
Me OTMS
Me
+
CHO
NMe 2
MeLi
Et 2O;
MeI
PhCHO, Et 3N, TMSCl
A *
OMe THF
MeO
90 °C
O
SnCl 4
MeNO 2
rt
53%
1) toluene
65 °C, 2 d
56%
2) MnO 2, CH 2Cl 2
25 °C, 12 h
96%
N
OMe
71%
CrO 3
py.
Et 2O
*theoretical ammount: 2.0 eq
1) t-BuLi,THF, -40°C,
then allyl bromide,
then CeCl 3 10%, r.t.
2) Dimethyldioxirane
69% over 2 steps
CH 2Cl 2
0 °C to rt
80%
CyCo(CO) 2
neat
reflux
45%
Ph
A
O
Ph
O
Me
Me
J. Barluenga et al., Org. Lett., 8, 2703 (2006)
TMS
TMS
O
H
H
N
OMe
K. P. C. Vollhardt et al., J. Am. Chem. Soc., 98, 6755 (1976)
SESNSO
BF 3·OEt 2
Cl(CH 2) 2Cl, 42 °C;
NaBH 3CN
t-AmOH, 0 °C
80%
SES = 2-(trimethylsilyl)ethanesulfonyl
A
C 13H 13NO 2
SES O
HN O H
S. M. Weinreb et al. J. Am. Chem. Soc. 112, 3475 (1990)
C 13H 23NO 2S
3) BnNHCH 2CO 2H
toluene, reflux, 12 h
68%
4) LiBH 4
THF/MeOH, reflux, 6 d
67%
BnN
N
H
OH
B. B. Snider et al., Tetrahedron Lett., 40, 3339 (1999)
3) P 4S 10, CH 2Cl 2,r.t.,90%
4)I 2, THF/H 2O, r.t., 98%
I
O
SCy
P. Metzner et al, Eur. J. Org. Chem., 1934 (2006)
O