Transition-Metal-Free α-Arylation of Enolizable Aryl Ketones and Mechanistic Evidence for a Radical Process

Martin Pichette Drapeau; Indira Fabre; Laurence Grimaud; Ilaria Ciofini; Thierry Ollevier; Marc Taillefer

doi:10.1002/anie.201502332

Transition-Metal-Free α-Arylation of Enolizable Aryl Ketones and Mechanistic Evidence for a Radical Process

Angew Chem Int Ed Engl. 2015 Sep 1;54(36):10587-91. doi: 10.1002/anie.201502332. Epub 2015 Jul 1.

Authors

Martin Pichette Drapeau^{1

2}, Indira Fabre^{3

4}, Laurence Grimaud³, Ilaria Ciofini⁴, Thierry Ollevier², Marc Taillefer⁵

Affiliations

¹ Institut Charles Gerhardt Montpellier, ENSCM, 8 rue de l'Ecole Normale, 34296 Montpellier (France).
² Département de chimie, Pavillon Alexandre-Vachon, Université Laval, 1045 avenue de la Médecine, Québec (Qc) G1V 0A6 (Canada).
³ UPMC-ENS-CNRS-UMR 8640, Ecole Normale Supérieure, Département de chimie 24 rue Lhomond, 75231 Paris (France).
⁴ Institut de Recherche de Chimie Paris, CNRS-Chimie ParisTech, 11 rue Pierre et Marie Curie, 75005 Paris (France).
⁵ Institut Charles Gerhardt Montpellier, ENSCM, 8 rue de l'Ecole Normale, 34296 Montpellier (France). marc.taillefer@enscm.fr.

PMID: 26136406
DOI: 10.1002/anie.201502332

Abstract

The α-arylation of enolizable aryl ketones can be carried out with aryl halides under transition-metal-free conditions using KOtBu in DMF. The α-aryl ketones thus obtained can be used for step- and cost-economic syntheses of fused heterocycles and Tamoxifen. Mechanistic studies demonstrate the synergetic role of base and solvent for the initiation of the radical process.

Keywords: CC coupling; arylation; ketones; reaction mechanisms.