Copper-catalyzed Asymmetric Cyclization of Alkenyl Diynes: Method Development and New Mechanistic Insights

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2021 Aug 5

PMID 34349921

Citations 9

Authors

Xin-Qi Zhu

Pan Hong

Yan-Xin Zheng

Ying-Ying Zhen

Feng-Lin Hong

Xin Lu

Long-Wu Ye

Affiliations

Soon will be listed here.

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(sp)-H functionalization, which constitutes the first asymmetric vinylic C(sp)-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 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.

Citing Articles

Asymmetric Büchner reaction and arene cyclopropanation via copper-catalyzed controllable cyclization of diynes.

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Asymmetric one-carbon ring expansion of diverse N-heterocycles via copper-catalyzed diyne cyclization.

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