Martin Silicates as Partners in Photoredox/Ni Dual Catalysis for the Installation of CH<sub>3</sub>, CH<sub>2</sub>D, CD<sub>2</sub>H, CD<sub>3</sub> and <sup>13</sup>CH<sub>3</sub> Groups onto (Hetero)Arenes
Mehdi Abdellaoui, Thomas Déis, Maxim‐Aleksa Wiethoff, Carlota Bahri, Gilles Lemière, Cyril Ollivier, Louis Fensterbank
Abstract
The introduction of a methyl group and its 13C and 2H labeled analogs on Csp2-centers remains a challenging issue in synthetic chemistry. While the photoredox/Ni dual catalysis has proven to constitute a valuable methodology for the forging of Csp2−Csp3 bonds, the high difficulty to generate the methyl radical and to control its reactivity has severely limited the development of reliable processes. Herein, we introduce the easily prepared and bench-stable Martin methylsilicates bearing two C,O-bidentate hexafluorocumyl alcohol ligands as a class of radical precursors for dual catalysis enabling the chemoselective methylation of (hetero)aryl halides and acyl chlorides as well as the access to the corresponding CD3, CD2H, CHD2 and 13CH3 analogs in good yields.