Reductive Asymmetric Aza‐Mislow‐Evans Rearrangement by 1,3,2‐Diazaphospholene Catalysis **
Abstract: 1,3,2‐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 of N‐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‐bound N,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.
- Standort
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Deutsche Nationalbibliothek Frankfurt am Main
- Umfang
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Online-Ressource
- Sprache
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Englisch
- Erschienen in
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Reductive Asymmetric Aza‐Mislow‐Evans Rearrangement by 1,3,2‐Diazaphospholene Catalysis ** ; day:15 ; month:03 ; year:2023 ; extent:6
Angewandte Chemie / International edition. International edition ; (15.03.2023) (gesamt 6)
- Urheber
- DOI
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10.1002/anie.202301076
- URN
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urn:nbn:de:101:1-2023031514323897636670
- Rechteinformation
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Letzte Aktualisierung
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14.08.2025, 10:52 MESZ
Datenpartner
Deutsche Nationalbibliothek. Bei Fragen zum Objekt wenden Sie sich bitte an den Datenpartner.
Beteiligte
- Zhang, Guoting
- Cramer, Nicolai
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