Using the Thiyl Radical for Aliphatic Hydrogen-Atom Transfer: Thiolation of Unactivated C-H Bonds

Liubov I Panferova; Mikhail O Zubkov; Vladimir A Kokorekin; Vitalij V Levin; Alexander D Dilman

doi:10.1002/anie.202011400

Using the Thiyl Radical for Aliphatic Hydrogen-Atom Transfer: Thiolation of Unactivated C-H Bonds

Angew Chem Int Ed Engl. 2021 Feb 8;60(6):2849-2854. doi: 10.1002/anie.202011400. Epub 2020 Dec 15.

Authors

Liubov I Panferova¹, Mikhail O Zubkov¹, Vladimir A Kokorekin¹, Vitalij V Levin¹, Alexander D Dilman¹

Affiliation

¹ N. D. Zelinsky Institute of Organic Chemistry, Leninsky prosp. 47, 119991, Moscow, Russian Federation.

PMID: 33146419
DOI: 10.1002/anie.202011400

Abstract

A metal- and catalyst-free thiyl-radical-mediated activation of alkanes is described. Tetrafluoropyridinyl disulfide is used to perform thiolation of the C-H bonds under irradiation with 400 nm light-emitting diodes. The key C-H activation step is believed to proceed via hydrogen-atom abstraction effected by the fluorinated thiyl radical. Secondary, tertiary, and heteroatom-substituted C-H bonds can be involved in the thiolation reaction. The resulting sulfides have wide potential as photoredox-active radical precursors in reactions with alkenes and heteroarenes.

Keywords: C−H functionalization; alkanes; photocatalysis; thiyl radicals; visible light.

Publication types

Research Support, Non-U.S. Gov't