Cobalt-Catalyzed α-Methoxymethylation and Aminomethylation of Ketones with Methanol as a C1 Source

Using methanol as a sustainable C1 source, cobalt-catalyzed alpha-methoxymethylation and alpha-aminomethylation of ketones have been developed. With cheap CoCl2 center dot 6H(2)O as catalyst and TBHP as oxidant, the methoxymethylated products were obtained within a short reaction time in up to 91% yield. Based on the observed reversibility of methoxy adduct to enone, the alpha-aminomethylation of ketones was then achieved by a one-pot methylenation/aza-Michael addition sequence. In addition, an easy way to convert alpha-methoxymethyl ketones to alpha-aminomethyl ketones has been discovered.