Ir‐Catalyzed Enantioselective Intra‐ and Intermolecular Formal C−H Conjugate Addition to β‐Substituted α,β‐Unsaturated Esters

An enantioselective intramolecular formal C−H conjugate addition of 4‐methyl 1‐aryl 2‐methylfumarates proceeded using a chiral iridium catalyst. A benzoylamide group served as a directing group, and chiral γ‐lactones with a quaternary all‐carbon stereogenic center were obtained with up to excellent ee. In the intermolecular reaction of N‐arylbenzamides with β‐substituted acrylates, C−H bond activation selectively occurred at the ortho‐position of carbonyl groups, and highly enantioselective formal C−H conjugate addition proceeded.