Enantioselective aza-Henry reaction using cinchona organocatalysts

被引：134

作者：

Bernardi, L

Fini, F

Herrera, RP

Ricci, A

Sgarzani, V

机构：

[1] Univ Bologna, Dept Organ Chem A Mangini, I-40136 Bologna, Italy

[2] Univ Alicante, Dept Quim Organ, E-03080 Alicante, Spain

来源：

TETRAHEDRON | 2006年 / 62卷 / 2-3期

关键词：

organocatalysis; imines; nitromethane; beta-nitroamines; aza-Henry reaction; cinchona alkaloids; enantioselectivity;

D O I：

10.1016/j.tet.2005.09.076

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The aza-Henry reaction of imines with nitromethane was promoted by cinchona alkaloids and modified cinchona bases to give optically active beta-nitroamines. Various N-protected imines were examined as substrates. N-Boc, N-Cbz, and N-Fmoc protected imines gave the best results in terms of chemical yields and enantioselectivities. After a careful screening of a series of chiral bases, very good enantioselectivities up to 94% ee were obtained using a cinchona-based thiourea organocatalyst under the optimized reaction conditions. (c) 2005 Elsevier Ltd. All rights reserved.

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页码：375 / 380

页数：6

相关论文

共 25 条

[1] The nitro-Mannich reaction and its application to the stereoselective synthesis of 1,2-diamines [J].

Adams, H ;

Anderson, JC ;

Peace, S ;

Pennell, AMK .

JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (26) :9932-9934

[2] Recent synthetic developments in the nitro to carbonyl conversion (Nef reaction) [J].

Ballini, R ;

Petrini, M .

TETRAHEDRON, 2004, 60 (05) :1017-1047

[3] Organocatalyzed solvent-free aza-Henry reaction:: A breakthrough in the one-pot synthesis of 1,2-diamines [J].

Bernardi, L ;

Bonini, BF ;

Capitò, E ;

Dessole, G ;

Comes-Franchini, M ;

Fochi, M ;

Ricci, A .

JOURNAL OF ORGANIC CHEMISTRY, 2004, 69 (23) :8168-8171

[4]

Enders D, 1996, SYNTHESIS-STUTTGART, P1443

[5] ADDITION OF AROMATIC THIOLS TO CONJUGATED CYCLOALKENONES, CATALYZED BY CHIRAL BETA-HYDROXY AMINES - A MECHANISTIC STUDY ON HOMOGENEOUS CATALYTIC ASYMMETRIC-SYNTHESIS [J].

HIEMSTRA, H ;

WYNBERG, H .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (02) :417-430

[6] Chiral amine-catalyzed asymmetric Baylis-Hillman reaction:: A reliable route to highly enantiomerically enriched (α-methylene-β-hydroxy)esters [J].

Iwabuchi, Y ;

Nakatani, M ;

Yokoyama, N ;

Hatakeyama, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (43) :10219-10220

[7]

Kacprzak K, 2001, SYNTHESIS-STUTTGART, P961

[8] A chiral molecular recognition approach to the formation of optically active quaternary centres in aza-Henry reactions [J].

Knudsen, KR ;

Jorgensen, KA .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2005, 3 (08) :1362-1364

[9] The first catalytic asymmetric aza-Henry reaction of nitronates with imines:: A novel approach to optically active β-nitro-α-amino acid- and α,β-diamino acid derivatives [J].

Knudsen, KR ;

Risgaard, T ;

Nishiwaki, N ;

Gothelf, KV ;

Jorgensen, KA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (24) :5843-5844

[10] Highly enantioselective conjugate addition of malonate and β-ketoester to nitroalkenes:: Asymmetric C-C bond formation with new bifunctional organic catalysts based on cinchona alkaloids [J].

Li, HM ;

Wang, Y ;

Tang, L ;

Deng, L .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (32) :9906-9907