[Chemical Science] 我室吕鑫教授和叶龙武教授发表论文:Copper-catalyzed asymmetric cyclization of alkenyl diynes: method development and new mechanistic insights

发布日期:2021年06月24日   浏览次数:

我室吕鑫教授和叶龙武教授在 Chemical Science 上发表论文:Copper-catalyzed asymmetric cyclization of alkenyl diynes: method development and new mechanistic insights

摘要: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 is proposed, thus providing new mechanistic insight into the copper-catalyzed asymmetric diyne cyclization and representing a new chiral control pattern in asymmetric catalysis based on remote-stereocontrol and vinyl cations. This method enables the practical and atom-economical construction of an array of valuable chiral polycyclic-pyrroles in high yields and enantioselectivities.

文章链接:https://pubs.rsc.org/en/content/articlelanding/2021/sc/d1sc02773e#!divAbstract