Enantioselective Intramolecular Hydroacylation of Unactivated Alkenes: An NHC‐Catalyzed Robust and Versatile Formation of Cyclic Chiral Ketones

A highly enantioselective intramolecular N-heterocyclic carbene (NHC)-catalyzed hydroacylation reaction gives access to a range of cyclic ketones from unactivated olefin-substituted aldehydes (up to 99 % ee). Remarkably, aliphatic aldehydes were also transformed efficiently in an NHC-catalyzed hydroacylation reaction for the first time.