Regio- and Stereoselective Photoredox-Catalyzed Atom Transfer Radical Addition of Thiosulfonates to Aryl Alkynes

Organic Letters
Zhiyuan PengTiezheng Jia

Abstract

Despite extensive investigations, altering the regioselectivity of atom transfer radical addition (ATRA) to alkynes remains a highly desirable yet unachieved challenge. Guided by computational predictions, thiosulfonates were found herein as a tunable radical precursor for thiyl radicals instead of well-recognized sulfonyl radicals. Merging such a finding with ATRA to phenylacetylenes leads to a highly regio- and stereoselective approach to (E)-β-arylsulfonylvinyl sulfides. This protocol is feathered by mild conditions, low photocatalyst loading, no transition-metal catalyst required, and broad functional group compatibility. The successful application of our protocol in the late-stage functionalization of bioactive natural product derivatives demonstrates its synthetic utility. Mechanistic studies corroborate the photoredox-catalyzed ATRA pathway and reveal the pivotal role of thiyl radical, to which unprecedented regioselectivity was attributed.

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