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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

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