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.
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Bibliographic citation
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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 ; (15.03.2023) (gesamt 6)
- Creator
- DOI
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10.1002/ange.202301076
- URN
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urn:nbn:de:101:1-2023031514350860894423
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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14.08.2025, 11:03 AM CEST
Data provider
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
- Zhang, Guoting
- Cramer, Nicolai
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Synergistic catalysis for cascade allylation and 2-aza-cope rearrangement of azomethine ylides
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Brønsted Acid Catalyzed Enantioselective Indole Aza-Claisen Rearrangement
Enantioselective PCCP Brønsted acid-catalyzed aza-Piancatelli rearrangement
Reductive Rearrangement of a 1‐Phospha‐2‐azanorbornene
Homopropargylic Ether Rearrangement via Gold Catalysis
Synthesis of Homoallylic Amines via 2-Aza-Cope Rearrangement
Tandem Acid/Pd‐Catalyzed Reductive Rearrangement of Glycol Derivatives
Unlocking Catalysis Using Oxidatively Induced Reductive Elimination
Homogenous and heterogeneous catalysis for non-reductive CO2 fixation