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Synthesis 2013; 45(10): 1406-1413
DOI: 10.1055/s-0032-1316917
DOI: 10.1055/s-0032-1316917
paper
(2S)-2-[(Phenylsulfinyl)methyl]pyrrolidine-Catalyzed Efficient Stereoselective Michael Addition of Cyclohexanone and Cyclopentanone to Nitroolefins
Further Information
Publication History
Received: 04 January 2013
Accepted after revision: 19 March 2013
Publication Date:
12 April 2013 (online)
Abstract
(2S)-2-[(Phenylsulfinyl)methyl]pyrrolidine, derived from l-proline, has been demonstrated as an efficient organocatalyst for the asymmetric Michael addition of cyclohexanone and cyclopentanone to β-nitrostyrenes. This pyrrolidine-based catalyst bearing a sulfoxide moiety was used to synthesize various γ-nitro carbonyl compounds in high yield (up to 97%) with excellent stereoselectivity (up to >99:1 dr and >99% ee) without the use of any additive.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis.
- Supporting Information
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For selected reviews on organocatalysis, see:
For reviews on organocatalytic asymmetric conjugate addition reactions, see:
For examples of asymmetric Michael additions of aldehydes and ketones to nitroolefins, see:
Wet toluene was obtained by shaking toluene (100 mL) with H2O (10 mL). The separated toluene layer was used as such in the reactions. Water is known to play a significant role in the enamine catalytic cycle, including in the regeneration of catalyst; see ref. 4e and:
We are grateful to the reviewers for pointing out our oversight in not elaborating on the chirality aspect of the sulfur atom in compounds 6 and 1. The proposed transition states have also been modified as per their suggestions. For Seebach’s model, see: