Photocatalytic C(sp3)-H Activation towards α-methylenation of Ketones using MeOH as 1 C Source Steering Reagent

Unprecedented direct access to terminal enones via alpha-methylenation of aryl ketones to form C=C bond is achieved under visible-light conditions using methanol as one carbon source substrate and solvent as well. The reaction involves Cu@g-C3N4-catalysed in situ oxidation of methanol into formaldehyde followed by dehydrative cross aldol type reaction. Various aryl ketones react efficiently with MeOH, producing alpha,beta-unsaturated carbonyl compounds only in 4-8 h at room temperature in excellent yield (84-97%). Operational simplicity, wide substrate scope, ambient reaction conditions, visible-light photocatalysis and novel application of MeOH as methylene donor substrate are the salient features making the envisaged protocol mild, efficient and green alternative to the existing methods for synthesis of such fine chemicals.