Herein we disclose the first example of the formal hydroacylation reactions of vinyl epoxides with chelating aldehydes enabled by rhodium catalysis for the efficient construction of functionalized esters. Detailed investigations of the mechanistic pathway reveal that the presence of a 2-vinyl group is essential in contributing to the success of this regioselective reaction, which might proceed through β-carbon cleavage as the key procedure.

A rhodium(I)-catalyzed regioselective hydroacylation of alkenyl-bearing allylic alcohols with simple aldehydes for the preparation of diverse 1,5-diketones is described. Mechanistic investigation suggests that this transformation might proceed through redox isomerization...

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.