Asymmetric Hydroacylation Involving Alkene Isomerization for the Construction of C3‐Chirogenic Center

Abstract A new transformation pattern for enantioselective intramolecular hydroacylation has been developed involving an alkene isomerization strategy. Proceeding through a five‐membered rhodacycle intermediate, 3‐enals were converted to C 3 ‐ or C 3 ,C 5 ‐chirogenic cyclopentanones with satisfactory yields, diastereoselectivities, and enantioselectivities. A catalytic cycle has been theoretically calculated and the origin of the stereoselection is rationally explained.