Nickel/Quinim Enabled Asymmetric Carbamoyl‐Acylation of Unactivated Alkenes

Abstract

Comprehensive SummaryTransition metal‐catalyzed difunctionalization of tethered alkene has emerged as a prevailing tool for the expedient construction of synthetically valuable cyclic compounds. However, most efforts have been devoted to the reaction of styrene‐type substrates due to their rigid scaffold and high reactivity. With respect to the difunctionalization of nonaromatic tethered olefin, especially the mono‐substituted alkene, still remains largely underdeveloped. Herein, we disclose a nickel/Quinim complex and TBADT‐cocatalyzed asymmetric carbamoyl‐acylation of unactivated alkene tethered on nonaromatic carbamoyl chlorides with diverse aldehydes. The reaction exhibits broad substrate scope with good functional group tolerance, as well as high reaction efficiency and enantioselectivity. Both monosubstituted and 1,1‐substituted alkenes can work well with either aliphatic or aromatic aldehydes under the current protocol, providing convenient access to an array of medicinally useful chiral γ‐lactams derivatives bearing a convertible acyl functionality. This reaction showcases more application possibilities of the chiral Quinim ligand in the future asymmetric catalytic transformations.