Dynamic Kinetic Resolution Allows Control of Remote Stereochemistry in Asymmetric Hydrogen Borrowing Alkylation

A catalytic asymmetric method for the synthesis of γ‐substituted ketones via hydrogen borrowing alkylation of both racemic linear precursors and 1,5‐diols is described. The base mediated racemization of an intermediate cyclohexenone facilities a dynamic kinetic resolution, affording highly enantioenriched cyclohexanes in excellent yields, which could be further functionalized by removal of the Ph* group. DFT modelling revealed the mode of enantioinduction to be a stepwise process comprising of a hydride transfer and a coordination change to a π‐allylic enolate complex with the iridium catalyst.