Enantioselective tandem Michael reaction to nitroalkene catalyzed by bifunctional thiourea: total synthesis of (-)-epibatidine

被引：113

作者：

Hoashi, Y ^{[1
]}

Yabuta, T ^{[1
]}

Yuan, P ^{[1
]}

Miyabe, H ^{[1
]}

Takemoto, Y ^{[1
]}

机构：

[1] Kyoto Univ, Grad Sch Pharmaceut Sci, Sakyo Ku, Kyoto 6068501, Japan

来源：

TETRAHEDRON | 2006年 / 62卷 / 2-3期

关键词：

thiourea organocatalyst; Michael addition; asymmetric synthesis; tandem reaction; nitroalkenes; (-)-epibatidine;

D O I：

10.1016/j.tet.2005.08.109

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Successive treatment of gamma,delta-unsaturated beta-ketoesters and nitroalkenes with a bifunctional thiourea and TMG promoted the tandem Michael addition, giving rise to highly functionalized cyclohexanones in good yields. The three contiguous stereogenic centers of the obtained products were constructed with high diastereo- and enantioselectivity (up to > 99% de and 92% ee). The reaction was successfully applied to the asymmetric synthesis of (-)-epibatidine, which was synthesized from the cyclohexanone derivative in seven steps in 30% overall yield. (c) 2005 Elsevier Ltd. All rights reserved.

引用

页码：365 / 374

页数：10

共 92 条

[1] Enantioselective Mannich-type reaction catalyzed by a chiral Bronsted acid
Akiyama, T
Itoh, J
Yokota, K
Fuchibe, K
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (12) : 1566 - 1568
[2] Dramatic improvement of the enantiomeric excess in the asymmetric conjugate addition reaction using new experimental conditions
Alexakis, A
Benhaim, C
Rosse, S
Humam, M
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (19) : 5262 - 5263
[3] Enantioselective copper-catalyzed conjugate addition of dialkyl zinc to nitro-olefins
Alexakis, A
Benhaim, C
[J]. ORGANIC LETTERS, 2000, 2 (17) : 2579 - 2581
[4] An approach to the narciclasine alkaloids via a quinone methide initiated cyclization reaction
Angle, SR
Wada, T
[J]. TETRAHEDRON LETTERS, 1997, 38 (46) : 7955 - 7958
[5] Asymmetric total synthesis of (-)-epibatidine
Aoyagi, S
Tanaka, R
Naruse, M
Kibayashi, C
[J]. TETRAHEDRON LETTERS, 1998, 39 (25) : 4513 - 4516
[6] Catalytic enantioselective synthesis of (-)-prostaglandin E1 methyl ester based on a tandem 1,4-addition-aldol reaction
Arnold, LA
Naasz, R
Minnaard, AJ
Feringa, BL
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2002, 67 (21) : 7244 - 7254
[7] BADIO B, 1994, MOL PHARMACOL, V45, P563
[8] Barco A, 2001, EUR J ORG CHEM, V2001, P975
[9] 2-AMINO-1,3-BUTADIENES AS CHIRAL BUILDING-BLOCKS - ENANTIOSELECTIVE SYNTHESIS OF 4-PIPERIDONES, 4-NITROCYCLOHEXANONES, AND 1,3-CYCLOHEPTADIONE DERIVATIVES
BARLUENGA, J
AZNAR, F
VALDES, C
MARTIN, A
GARCIAGRANDA, S
MARTIN, E
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (10) : 4403 - 4404
[10] Cycloaddition reactions of chiral 2-amino-1,3-butadienes with nitroalkenes: Synthesis of enantiomerically pure 4-nitrocyclohexanones
Barluenga, J
Aznar, F
Ribas, C
Valdes, C
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (20) : 6746 - 6753

← 1 2 3 4 5 6 7 8 9 10 →