Radical–Radical Cross-Coupling for C–S Bond Formation - Organic Letters (ACS Publications)

Radical–Radical Cross-Coupling for C–S Bond Formation - Organic Letters (ACS Publications)

Zhiliang Huang^†, Dongchao Zhang^†, Xiaotian Qi^‡, Zhiyuan Yan^†, Mengfan Wang^†, Haiming Yan^|, and Aiwen Lei^*†|

^† College
of Chemistry and Molecular Sciences, Institute for Advanced Studies
(IAS), Wuhan University, Wuhan 430072, People’s Republic of China

^‡ School
of Chemistry and Chemical Engineering, Chongqing
University, Chongqing 400030, People’ s Republic of China

^| National
Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang 330022, People’ s Republic
of China

Org. Lett., Article ASAP

DOI: 10.1021/acs.orglett.6b00764

Publication Date (Web): May 6, 2016

Copyright © 2016 American Chemical Society

*E-mail: aiwenlei@whu.edu.cn.

Abstract

A
new method was demonstrated to overcome the selectivity issue of
radical–radical cross-coupling toward the synthesis of asymmetric diaryl
thioethers. The preliminary mechanism was revealed by radical-trapping
experiments, DFT calculations, and kinetics, etc., indicating that the
C–S bond formed through cross-coupling of a thiyl radical and an aryl
radical cation. Moreover, the formation of an aryl radical cation
instead of the C–H bond cleavage was determined as the rate-limiting
step.