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.

Automated summary

The introduction of methyl group and its labeled analogs on Csp(2)-centers is a challenging issue in synthetic chemistry. The difficulty to generate methyl radical and control its reactivity limits the development of reliable processes. In this study, we introduce Martin methylsilicates with hexafluorocumyl alcohol ligands as radical precursors for chemoselective methylation, enabling the access to various analogs in good yields.