New insights into the mechanism of synergetic photoredox/copper(i)-catalyzed carbocyanation of 1,3-dienes: a DFT study.

ABSTRACT: This work presents a DFT-based computational study to understand the mechanism, and regio- and enantioselectivities in the synergetic photoredox/copper(i)-catalyzed carbocyanation of 1,3-dienes with alkyl redox-active esters. The calculated results show an unprecedented copper catalytic mechanism, where the reaction follows a catalytic cycle involving Cu^I-only catalysis, instead of a Cu(i)/Cu(ii)/Cu(iii)/Cu(i) cycle as proposed in the experimental study. Moreover, it is found that the critical step involves the reaction of the cyanocopper(i) species with an allyl cation rather than the cyanocopper(ii) species reacting with an allyl radical as proposed in the experiment, and that the photocatalyst is regenerated via single electron transfer from the allyl radical to the ox

SUBMITTER: Liu Y 

PROVIDER: S-EPMC10155915 | biostudies-literature | 2023 May

REPOSITORIES: biostudies-literature