The use of N-alkyl-2,2'-bipyrrolidine derivatives as organocatalysts for the asymmetric Michael addition of ketones and aldehydes to nitroolefins

Andrey, Olivier; Alexakis, Alexandre; Tomassini, Axel; Bernardinelli, Gérald Hugues

doi:10.1002/adsc.200404037

Scientific article

English

The use of N-alkyl-2,2'-bipyrrolidine derivatives as organocatalysts for the asymmetric Michael addition of ketones and aldehydes to nitroolefins

Contributors

Andrey, Olivier; Alexakis, Alexandre; Tomassini, Axel; Bernardinelli, Gérald Hugues

Published in

Advanced synthesis & catalysis, vol. 346, no. 9-10, p. 1147-1168

Publication date

2004

Abstract

The direct Michael addition of aldehydes and ketones to nitroolefins, catalyzed by N-i-Pr-2,2'-bipyrrolidine, is described. The desired 1,4-adducts are obtained in excellent yields with enantioselectivities up to 95% ee and dr up to 95 : 5 of the syn aldehyde addition product. An unexpected inversion of diastereoselectivity was observed for the addition of a-hydroxy ketones to ß-arylnitroolefins with enantioselectivities up to 98% ee. The formation of an internal hydrogen bond between the OH group of the a-hydroxy ketone and the tertiary nitrogen of the catalyst leads to the formation of a rigid cis enamine intermediate that accounts for the inversion of the expected diastereoselectivity and the very high ees.

Keywords

Amines
Asymmetric catalysis
Conjugate addition
Nitroolefins
Organocatalysis

Note

Special Issue : Organic Catalysis

UNIGE affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

Citation (ISO format)

ANDREY, Olivier et al. The use of N-alkyl-2,2′-bipyrrolidine derivatives as organocatalysts for the asymmetric Michael addition of ketones and aldehydes to nitroolefins. In: Advanced synthesis & catalysis, 2004, vol. 346, n° 9-10, p. 1147–1168. doi: 10.1002/adsc.200404037

Article (Published version)

Identifiers

PID : unige:8215
DOI : 10.1002/adsc.200404037

Journal ISSN

1615-4150

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21/06/2010 14:44:41

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21/06/2010 14:44:41

Update

14/03/2023 15:48:36

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14/03/2023 15:48:36

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29/10/2024 15:35:36

The use of N-alkyl-2,2'-bipyrrolidine derivatives as organocatalysts for the asymmetric Michael addition of ketones and aldehydes to nitroolefins

Contributors

Published in

Publication date

Abstract

Keywords

Note

UNIGE affiliation entities

Citation (ISO format)

Main files (1)

Identifiers

Journal ISSN

Technical informations

Creation

First validation

Update

Status update

Last indexation