Copper-catalyzed asymmetric cyclization of alkenyl diynes: method development and new mechanistic insights.

ABSTRACT: Metal carbenes have proven to be one of the most important and useful intermediates in organic synthesis, but catalytic asymmetric reactions involving metal carbenes are still scarce and remain a challenge. Particularly, the mechanistic pathway and chiral induction model in these asymmetric transformations are far from clear. Described herein is a copper-catalyzed asymmetric cyclization of alkenyl diynes involving a vinylic C(sp²)-H functionalization, which constitutes the first asymmetric vinylic C(sp²)-H functionalization through cyclopentannulation. Significantly, based on extensive mechanistic studies including control experiments and theoretical calculations, a revised mechanism involving a novel type of endocyclic copper carbene via remote-stereocontrol i

SUBMITTER: Zhu XQ 

PROVIDER: S-EPMC8278876 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature