Photocatalytic Methylation of Nonactivated sp<sup>3</sup> and sp<sup>2</sup> C–H Bonds Using Methanol on GaN
Mingxin Liu, Zihang Qiu, Lida Tan, Roksana Tonny Rashid, Sheng Chu, Yunen Cen, Ziling Luo, Rustam Z. Khaliullin, Zetian Mi, Chao‐Jun Li
Abstract
Although the development of C–H functionalization methods has enlightened many reactivities in chemistry, the direct functionalization of unactivated C–H bonds, which are particularly common in petroleum compounds, is still faced with great difficulty. Herein, we describe a photocatalytic approach that allows direct methylation of unactivated sp3 and sp2 C–H bonds using methanol as the methylation reagent, with gallium nitride as a powerful yet robust catalyst. Mechanistic studies suggested that the methanol is dehydrated into methyl carbene intermediate via a bimolecular mechanism.
Topics & Concepts
MethanolCatalysisChemistryPhotocatalysisReagentSurface modificationMethylationCarbenePhotochemistryGalliumNitrideOrganic chemistryPhysical chemistryLayer (electronics)BiochemistryGeneCatalytic C–H Functionalization MethodsSynthesis and Catalytic ReactionsAsymmetric Hydrogenation and Catalysis