Issue 3, 2023

Photochemical halogen-bonding assisted generation of vinyl and sulfur-centered radicals: stereoselective catalyst-free C(sp2)–S bond forming reactions

Abstract

The combination of photochemistry and halogen bonding interactions has risen in the last few years as a powerful synthetic tool for the creation of radical intermediates under mild conditions. In the formation of carbon-centered radicals, this reactivity has been to date restricted to the employment of aryl and alkyl halides as precursors. We now envisioned that the halogen-bonding initiated formation of highly reactive vinyl radicals would be a feasible process for the photochemical cross-coupling between thiols and alkenyl halides under basic conditions. The reaction shows indeed a very broad functional group tolerance, is stereoselective, simple and scalable. In-depth mechanistic studies point at the formation of vinyl and sulfur-centered radicals as the intermediates of the reaction and DFT calculations support the pre-formation of a halogen-bonding complex as the initiator of the photochemical transformation. Synthetic applications were developed to extend the utility of this methodology.

Graphical abstract: Photochemical halogen-bonding assisted generation of vinyl and sulfur-centered radicals: stereoselective catalyst-free C(sp2)–S bond forming reactions

Supplementary files

Article information

Article type
Edge Article
Submitted
07 Okt 2022
Accepted
06 Dez 2022
First published
07 Dez 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 650-657

Photochemical halogen-bonding assisted generation of vinyl and sulfur-centered radicals: stereoselective catalyst-free C(sp2)–S bond forming reactions

H. F. Piedra and M. Plaza, Chem. Sci., 2023, 14, 650 DOI: 10.1039/D2SC05556B

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