Rhodium‐Catalyzed Decarboxylative Hydroacylation of Vinylethylene Carbonates for Regioselective Ester Synthesis

Abstract

A rhodium(I)‐catalyzed decarboxylative hydroacylation of readily available vinylethylene carbonates with salicylaldehydes for regioselective preparation of esters was developed. Reaction optimization revealed that methacrylamide might promote the hydroacylation by bidentate chelation assistance to the cationic rhodium. Mechanistic findings suggested that this one‐pot coupling reaction proceeds via Markovnikov hydrorhodation‐initiated site‐selective β‐C−O bond cleavage with concurrent release of CO2.

Rhodium(I) Catalyzed Hydroacylation Reactions of Alkenyl Compounds

“…Accordingly, the decarboxylative hydroacylation of VECs enabled by the Rh(I) catalysis for the site‐selective synthesis of various esters 100 was developed in our group (Scheme 18). [73] The existence of methacrylamide L2 was beneficial in promoting the conversion. Meanwhile, this strategy can tolerate a broad range of the aryl‐substituted VECs as well as the salicylaldehyde components with electron‐rich and electron‐poor substituents.…”