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Issue 27, 2021
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Copper-catalyzed asymmetric cyclization of alkenyl diynes: method development and new mechanistic insights

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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 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.

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

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Supplementary files

Article information


Submitted
21 May 2021
Accepted
11 Jun 2021
First published
11 Jun 2021

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2021,12, 9466-9474
Article type
Edge Article

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

X. Zhu, P. Hong, Y. Zheng, Y. Zhen, F. Hong, X. Lu and L. Ye, Chem. Sci., 2021, 12, 9466 DOI: 10.1039/D1SC02773E

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