Dynamic Kinetic Resolution of Aldehydes by Hydroacylation

We report a dynamic kinetic resolution (DKR) of chiral 4‐pentenals by olefin hydroacylation. A primary amine racemizes the aldehyde substrate via enamine formation and hydrolysis. Then, a cationic rhodium catalyst promotes hydroacylation to generate α,γ‐disubstituted cyclopentanones with high enantio‐ and diastereoselectivities.     

Cobalt‐Catalyzed Enantio‐ and Diastereoselective Intramolecular Hydroacylation of Trisubstituted Alkenes

Enantio‐ and diastereoselective synthesis of trans ‐2,3‐disubstituted indanones is achieved by intramolecular hydroacylation of 2‐alkenylbenzaldehydes bearing trisubstituted alkenyl groups under cobalt‐chiral diphosphine catalysis. Notably, a high level of enantioselectivity is induced regardless of the stereochemistry (E /Z ratio) of the alkenyl group of the starting material. Deuterium‐labeling experiments shed light on the productive reaction pathways of the E ‐ and Z ‐isomers.