Reductive Asymmetric Aza‐Mislow‐Evans Rearrangement by 1,3,2‐Diazaphospholene Catalysis**

Author:

Zhang Guoting1ORCID,Cramer Nicolai1ORCID

Affiliation:

1. Institute of Chemical Sciences and Engineering (ISIC), EPFL SB ISIC LCSA, BCH 4305 1015 Lausanne Switzerland

Abstract

Abstract1,3,2‐diazaphospholene hydrides (DAP−H) enable smooth conjugate reduction of polarized double bonds. The transiently formed phosphorus‐enolate provides a potential platform for reductive α‐functionalizations. In this respect, asymmetric C‐heteroatom bond forming processes are synthetically appealing but remain elusive. We report a 1,3,2‐diazaphospholene‐catalyzed three‐step cascade reaction ofN‐sulfinyl acrylamides comprised of conjugate reduction, [2,3]‐sigmatropic aza‐Mislow‐Evans rearrangement and subsequent S−O bond cleavage. The obtained enantio‐enriched α‐hydroxy amides are formed in good yields and excellent enantiospecificity. The stereo‐defined P‐boundN,O‐ketene aminal ensures an excellent transfer of chirality from the sulfur stereocenter to α‐carbon. The transformation operates under mild conditions at ambient temperature. Moreover, DAP−H is a competent reductant for the cleavage of formed sulfenate ester, eliminating the extra step in traditional Mislow‐Evans processes.

Funder

Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung

Publisher

Wiley

Subject

General Medicine

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