Boosting N-Heterocyclic Carbene Radical Organocatalysis with Nickel Chemistry: A Rational Mechanistic Study-based Approach - Département de Chimie Moléculaire Accéder directement au contenu
Article Dans Une Revue (Article De Synthèse) ACS Catalysis Année : 2024

Boosting N-Heterocyclic Carbene Radical Organocatalysis with Nickel Chemistry: A Rational Mechanistic Study-based Approach

Résumé

A cooperative NHC/nickel catalytic methodology has been developed for the synthesis of ketones employing aromatic aldehydes and tertiary alkyl iodides. All key steps of the postulated catalytic cycle were validated with comprehensive stoichiometric and electrochemical studies, including reduction of Ni$^I$$^I$ by the deprotonated Breslow intermediate, Ni$^0$ promoted halogen-atom abstraction to generate transient tertiary alkyl radicals, and coupling between the latter with the persistent acyl thiazolium radical intermediate. Such a broadly proposed and accepted, yet elusive, acyl thiazolium radical intermediate has been isolated and studied by a single-crystal X-ray diffraction study.
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Dates et versions

hal-04570741 , version 1 (07-05-2024)

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Ludivine Delfau, Elena Mauro, Jacques Pecaut, David Martin, Eder Tomás-Mendivil. Boosting N-Heterocyclic Carbene Radical Organocatalysis with Nickel Chemistry: A Rational Mechanistic Study-based Approach. ACS Catalysis, 2024, 14 (9), pp.7149-7156. ⟨10.1021/acscatal.4c01253⟩. ⟨hal-04570741⟩
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