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

Using methanol as a sustainable C1 source, cobalt-catalyzed α-methoxymethylation and α-aminomethylation of ketones have been developed. With cheap CoCl₂·6H₂O 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 α-aminomethylation of ketones was then achieved by a one-pot methylenation/aza-Michael addition sequence. In addition, an easy way to convert α-methoxymethyl ketones to α-aminomethyl ketones has been discovered.