Martin Silicates as Partners in Photoredox/Ni Dual Catalysis for the Installation of CH3, CH2D, CD2H, CD3 and 13CH3 Groups onto (Hetero)Arenes

The introduction of a methyl group and its C-13 and H-2 labeled analogs on Csp(2)-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 Csp(2)-Csp(3) 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 (CH3)-C-13 analogs in good yields.