ID | 65231 |
FullText URL | |
Author |
Rozsar, Daniel
Department of Chemistry, University of Oxford, Chemistry Research Laboratory
Farley, Alistair J. M.
Department of Chemistry, University of Oxford, Chemistry Research Laboratory
McLauchlan, Iain
Department of Chemistry, University of Oxford, Chemistry Research Laboratory
Shennan, Benjamin D. A.
Department of Chemistry, University of Oxford, Chemistry Research Laboratory
Yamazaki, Ken
Division of Applied Chemistry, Okayama University
Dixon, Darren J.
Department of Chemistry, University of Oxford, Chemistry Research Laboratory
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Abstract | Herein we describe the enantioselective intermolecular conjugate addition of nitroalkanes to unactivated α,β-unsaturated esters, catalyzed by a bifunctional iminophosphorane (BIMP) superbase. The transformation provides the most direct access to pharmaceutically relevant enantioenriched γ-nitroesters, utilizing feedstock chemicals, with unprecedented selectivity. The methodology exhibits a broad substrate scope, including β-(fluoro)alkyl, aryl and heteroaryl substituted electrophiles, and was successfully applied on a gram scale with reduced catalyst loading, and, additionally, catalyst recovery was carried out. The formal synthesis of a range of drug molecules, and an enantioselective synthesis of (S)-rolipram were achieved. Additionally, computational studies revealed key reaction intermediates and transition state structures, and provided rationale for high enantioselectivities, in good agreement with experimental results.
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Keywords | Asymmetric Catalysis
C-C Bond Formation
Conjugate Addition
Enantioselective Synthesis
Organocatalysis
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Published Date | 2023-04-13
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Publication Title |
Angewandte Chemie International Edition
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Volume | volume62
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Issue | issue21
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Publisher | Wiley
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Start Page | e202303391
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ISSN | 1433-7851
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Content Type |
Journal Article
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language |
English
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OAI-PMH Set |
岡山大学
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Copyright Holders | © 2023 The Authors.
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File Version | publisher
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PubMed ID | |
DOI | |
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Related Url | isVersionOf https://doi.org/10.1002/anie.202303391
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License | http://creativecommons.org/licenses/by/4.0/
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