Fukuyama Group - Group Meeting Problems 03/02/2005
Fukuyama Group - Group Meeting Problems 03/02/2005
Fukuyama Group - Group Meeting Problems 03/02/2005
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<strong>Fukuyama</strong> <strong>Group</strong> - <strong>Group</strong> <strong>Meeting</strong> <strong>Problems</strong><br />
<strong>03</strong>/<strong>02</strong>/<strong>2005</strong><br />
OEt<br />
TBS<br />
H<br />
O<br />
O<br />
BnN t-BuOK<br />
NBn<br />
O2, P(OEt) 3 silica gel O<br />
H<br />
N<br />
O<br />
O<br />
1) BrCCl 3, DBU, CCl 4, hν, 85%<br />
2) n BuCu(CN)Li, THF, –30 °C; AcOH-THF, 80%<br />
3) LDA, 1-acetylcyclopentene, THF, –80 °C to 0 °C, 48%<br />
O<br />
N<br />
H<br />
NH 2<br />
O<br />
OMe<br />
aq. CH 2O<br />
PhSH<br />
Et 3N<br />
EtOH<br />
reflux<br />
73%<br />
t-BuOH-monoglyme<br />
–20 °C;<br />
PCl 5 (2 eq)<br />
toluene<br />
reflux, 4 h<br />
63%<br />
DMAP (5 mol%)<br />
HOCH 2CH 2OH<br />
0 °C to rt, 24 h<br />
81%<br />
C 12H 12OS<br />
96%<br />
PhCH 2CN (1 eq)<br />
NaH (3 eq)<br />
THF<br />
reflux, 12 h<br />
83%<br />
1 H-NMR: δ 7.17-7.51 (m, 6H),<br />
3.68 (d, 2H), 2.42-2.56 (m, 4H)<br />
TMSCH 2OTf<br />
CH 3CN;<br />
CsF<br />
54%<br />
HO<br />
O NH 2<br />
Büchi, G. et al., J. Am. Chem. Soc., 92, 999 (1970)<br />
N<br />
H<br />
O<br />
SPh<br />
Cohen, T. et al., J. Org. Chem., 50, 2965 (1985)<br />
N<br />
Ph<br />
Langer, P. et al., Eur. J. Org. Chem., 5<strong>02</strong>0 (2004)<br />
O O<br />
H<br />
O<br />
OMe<br />
TBSO<br />
n Bu<br />
Takeda, K. et al., Org, Lett., 1, 677 (1999)<br />
Connon, S. T. et al., Chem. Comm., 227 (<strong>2005</strong>)<br />
O
1<br />
2<br />
MeO<br />
3<br />
4<br />
5<br />
<strong>Fukuyama</strong> <strong>Group</strong> - <strong>Group</strong> <strong>Meeting</strong> <strong>Problems</strong><br />
<strong>03</strong>/08/<strong>2005</strong><br />
OMe<br />
O<br />
O<br />
O<br />
OH<br />
MeO OMe<br />
N<br />
DMF<br />
80 °C, 3 h;<br />
cyanoacetamide<br />
DMF<br />
100 °C, 3 h<br />
PPh 3<br />
Br<br />
N<br />
Me<br />
N<br />
H<br />
29%<br />
O<br />
N<br />
H<br />
1) propargyl bromide<br />
K 2CO 3, LiBr, n Bu 4N + Br -<br />
PhMe/H 2O<br />
100 °C, 1 h<br />
2) AcOH/HCl/H 2O<br />
60 °C, 1 h<br />
86% (2 steps)<br />
1) 160 °C<br />
2) LDA (1.1 eq), THF;<br />
ClCO 2Et (1.1 eq)<br />
3) NaBF 4<br />
(counter anion exchange)<br />
H<br />
O O<br />
H<br />
N<br />
O<br />
(thf)W(CO) 5<br />
(25 mol%)<br />
CO 2Me<br />
THF, rt<br />
90%<br />
1) Tf 2O, DTBMP*<br />
CH 2Cl 2, 95%<br />
2) LAH, Et 2O<br />
0 °C, 64%<br />
NaH; A<br />
HCl<br />
acetone, rt<br />
98%<br />
A<br />
aniline<br />
Dy(OTf) 3 (10 mol%)<br />
MeCN<br />
50 °C, 16 h<br />
71%<br />
Batey, R. A. et al., Org, Lett., 6, 4913 (2004)<br />
O<br />
CO 2Et<br />
Dauben, W. G. et al., J. Am. Chem. Soc., 99, 7307 (1977)<br />
1) TsCl, Et 3N, CH 2Cl 2, 83%<br />
2) 4-ethyl-4-pentenoic acid<br />
WSCD•HCl, DMAP, CH 2Cl 2, 87%<br />
3) o-dichlorobenzene<br />
180-190 °C, 74%<br />
HO<br />
O<br />
Barluenga, J. et. al., Angew. Chem. Int. Ed., 44, 126 (<strong>2005</strong>)<br />
1) Tf 2O<br />
CH 2Cl 2<br />
0 °C<br />
N<br />
Me<br />
N<br />
N<br />
O<br />
O<br />
CO 2Me<br />
N<br />
O<br />
CN<br />
Boger, D. L. et al., Org. Lett., 7, 741 (<strong>2005</strong>)<br />
O 3) mCPBA 2) CH3CN, reflux;<br />
O<br />
CH AcHN<br />
2Cl2, 78% sat. NaHCO3, 85%<br />
*2,6-di-t-butyl-4-methylpyridine<br />
Maritinez, A. G. et al., J. Org. Chem., 68, 1451 (20<strong>03</strong>)<br />
Maritinez, A. G. et al., Tetrahedron, 61, 599 (<strong>2005</strong>)
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<strong>Fukuyama</strong> <strong>Group</strong> - <strong>Group</strong> <strong>Meeting</strong> <strong>Problems</strong><br />
<strong>03</strong>/16/<strong>2005</strong><br />
O<br />
MeO<br />
MeO<br />
O<br />
O<br />
OMe<br />
O<br />
CO 2Me<br />
CO 2Me<br />
N<br />
N<br />
N<br />
H<br />
OH<br />
N 2<br />
Ox<br />
H<br />
1)<br />
NHAc<br />
O 2N<br />
CHO<br />
48%<br />
O<br />
N<br />
1) N 2H 4 (2 eq)<br />
EtOH<br />
NO 2<br />
2) NaNO 2, HCl;<br />
Δ, 16 h<br />
69% (3 steps)<br />
ONH 2<br />
PhMe, reflux<br />
90%<br />
1) TosMIC (1 eq)<br />
K 2CO 3 (1 eq)<br />
MeOH, reflux, 1 h<br />
2) KOH (xs)<br />
MeOH, reflux, 3 h<br />
64% (2 steps)<br />
2) Pb(OAc) 4<br />
Rh(OAc) 2<br />
DMAD<br />
70%<br />
Ph<br />
N O<br />
–50 °C, CH 2Cl 2<br />
57%<br />
1) MeI, aq. NaOH<br />
2) Ag(OH) 2, H 2O<br />
50 ºC, 0.5 h<br />
Murata, I. et. al., Tetrahedron Lett., 35, 8421 (1994)<br />
O<br />
O<br />
Padwa, A. et al., J. Org. Chem., 60, 53 (1995)<br />
Ox<br />
P. A. Jacobi et al., Tetrahedron Lett., 29, 6865 (1988)<br />
o-dichlorobenzene<br />
reflux, 40 h<br />
70%<br />
MeO 2C<br />
MeO 2C<br />
O O<br />
O<br />
C 8H 8<br />
1 H NMR:<br />
4.60(m, 2H)<br />
6.63(sextet, 6H)<br />
O<br />
N H<br />
O<br />
MeO<br />
MeO<br />
Ox =<br />
hν, Me 2CO<br />
OMe<br />
J. K. Cha et al., Tetrahedron, 56, 10175 (2000)<br />
O<br />
N<br />
semibullvalene<br />
Zimmerman, H. E. et al., J. Am. Chem. Soc., 91, 2330 (1969)<br />
Zimmerman, H. E. et al., J. Am. Chem. Soc., 91, 3316 (1969)<br />
O<br />
NHAc
1<br />
2<br />
Ph<br />
3<br />
4<br />
5<br />
O<br />
<strong>Fukuyama</strong> <strong>Group</strong> - <strong>Group</strong> <strong>Meeting</strong> <strong>Problems</strong><br />
<strong>03</strong>/23/<strong>2005</strong><br />
O<br />
HO<br />
Me<br />
O<br />
N 2<br />
PtCl 2 (5 mol%)<br />
toluene, 80 °C<br />
O<br />
O<br />
SO 2Ph<br />
N 2<br />
84%<br />
O<br />
OMe<br />
O<br />
Cl<br />
TMS<br />
CO 2Et<br />
CO2Et BuLi<br />
THF<br />
–78 °C to rt<br />
83%<br />
tricyclo compound<br />
(except for Ph group)<br />
1) PhSCl, Et 3N<br />
THF, –78 ºC<br />
2) m-CPBA<br />
CH 2Cl 2, 0 ºC<br />
Rh 2(OOct) 4<br />
CH 2Cl 2<br />
20%<br />
Rh 2(OAc) 4<br />
PhH, 80°C<br />
85% (2 steps)<br />
HO<br />
OH O<br />
DBU<br />
benzene<br />
reflux<br />
92%<br />
TBSOTf<br />
Et 3N<br />
CH 2Cl 2<br />
O<br />
OMe<br />
aq. HCl<br />
THF, reflux<br />
72%<br />
DDQ (2 eq)<br />
CH 2Cl 2-H 2O, 40 °C<br />
60%<br />
Ph<br />
A. M. Echavarren et al. Org. Lett. 6, 3191 (2004)<br />
cat. [RhCl(CO)dppp] 2<br />
CO (1 atm)<br />
toluene<br />
reflux<br />
97%<br />
O<br />
O<br />
H<br />
Ph<br />
O<br />
O<br />
SO 2Ph<br />
CO 2Et<br />
CO 2Et<br />
S. Koo et al. Tetrahedron Lett. 45, 7<strong>02</strong>3 (2004)<br />
TMS<br />
C. Murai et al. J. Org. Chem. 68, 1376 (20<strong>03</strong>)<br />
toluene<br />
65 °C<br />
55%<br />
(2 steps)<br />
O<br />
O<br />
OTBS<br />
H. M. L. Davies et al. J. Org. Chem. 65, 4261 (2000)<br />
BF 3·OEt 2<br />
PhH OMe<br />
HO<br />
John L Wood et al., J. Am. Chem. Soc., 117, 10413 (1995)<br />
O<br />
O<br />
O