Bifunctional Iminophosphorane‐Catalyzed Enantioselective Nitroalkane Addition to Unactivated α,β‐Unsaturated Esters **

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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.

Location: Deutsche Nationalbibliothek Frankfurt am Main

Extent: Online-Ressource

Language: Englisch

Bibliographic citation: Bifunctional Iminophosphorane‐Catalyzed Enantioselective Nitroalkane Addition to Unactivated α,β‐Unsaturated Esters ** ; day:13 ; month:04 ; year:2023 ; extent:10
Angewandte Chemie ; (13.04.2023) (gesamt 10)

Creator: Rozsar, Daniel
Farley, Alistair J. M.
McLauchlan, Iain
Shennan, Benjamin D. A.
Yamazaki, Ken
Dixon, Darren

DOI: 10.1002/ange.202303391

URN: urn:nbn:de:101:1-2023041315325940494966

Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.

Last update: 14.08.2025, 10:50 AM CEST

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Associated

Rozsar, Daniel
Farley, Alistair J. M.
McLauchlan, Iain
Shennan, Benjamin D. A.
Yamazaki, Ken
Dixon, Darren

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