Fukuyama Group - Group Meeting Problems 06/14/2008

1
2
BocHN CO 2H
Br
3
4
Ph
Ph
Bn
S
N
CN
Fukuyama Group - Group Meeting Problems
06/14/2008
OMe
OH
NH 2
C 7H 8O 2
1) HBTU
DIPEA
CH 2Cl 2
95%
2) TFA
CH 2Cl 2
MeSPh
A
n-Pr
HgO (yellow)
Na 2SO 4
3) HBTU, DIPEA
A, CH 2Cl 2;
TFA
84% (2 steps)
4) Oxone
DMF, H 2O
BocN
FmocHN CO 2H
Me
ether, rt
O
CO 2i-Pr
1) PhI(OAc) 2 (1.2 eq)
MeOH, 0 °C, 97%
2) NaH, Me 3S(O)I
DMSO, 62%
3) 10% HCl(aq.)
MeOH, 88%
B
DMF
40 °C
41% (2 steps)
Me
B
LDA
THF
−78 °C to rt
87%
C 7H 6O 2
Ph
cat. 2-anilinonaphthalene*
neat, rt
81%
HOHN
·oxalate
O
FmocHN
H
N CO 2tBu
Me
HN
O
H
N
Bn
O
N
H
Me
O
H
N CO 2t-Bu
Me
Me
Me
J. W. Bode et al., J. Am. Chem. Soc., 130, 4253 (2008)
decane
180 °C
74%
OH
CO2i-Pr Me
M. Hiersemann, Eur. J. Org. Chem., 2001, 483
4) SPh , t-BuOLi, THF
−60 °C, 48%
O
O
TsOH
200 °C, 10 min
55%
*polymerization inhibitor
J. B. Miller, J. Org. Chem., 24, 560 (1959)
R. Huisgen et al., Helv. Chim. Acta, 91, 783 (2008)
5) K 2CO 3, Me 2SO 4
acetone, reflux, 65%
6) Zn, AcOH
reflux, 66%
Me
Ph
OMe
OMe
C 17H 16O 4
D. Mal et al., Eur. J. Org. Chem., 2008, 3014
O
O

1
2
3
4
Fukuyama Group - Group Meeting Problems
06/18/2008
Br
t-BuOK*
DMSO
66%
*theoretical amount: 1 eq.
Me
Ph O O
O
HO
HO
Br
TMS
Mn(OAc) 3·2H 2O*
Cu(OAc) 2*, KOAc
AcOH, 70 °C
62%
*theoretical amount: 1 eq.
O TMS
1)
CHBr 3*
KOH* (powder)
TEBACl (cat.)
CH 2Cl 2
0 °C to rt
80%
MeLi*
Et 2O
0 °C
84%
NO
N
NH 2
O
NaOMe (ex.)
pentane
0 °C
36%
A. de Meijere et al., Angew. Chem. Int. Ed., 30, 1518 (1991)
SnBu 3
Pd(PPh 3) 4
toluene, 85 °C
62%
bicyclic compound
except for Ph
Br
t-BuLi, CeCl 3
67% + diastereomer 13%
2) MeLi (0.1 eq)
Ph 2O, 195 °C, 1 h;
acidic workup
85%
HO
OH
H
TMS
C. Bour et al., Tetrahedron, 62, 10567 (2006)
1) Mg(ClO 4) 2
BnOH, 120 °C, 80%
2) NaN 3, Tf 2O, TBAB
2N NaOH aq.-n-Hex-MeCN
0 °C, 92%
3) Rh 2(OAc) 4
CH 2Cl 2
89%
H
Ph
O Ph
G. Bruton et al., J. Org. Chem., 69, 122 (2004)
H
O
T. V. Ovaska et al., Tetrahedron Lett., 39, 5705 (1998)
*
H
O
H
O