Issue 1, 2020

Sulfamides direct radical-mediated chlorination of aliphatic C–H bonds

Abstract

Given the prevalence of aliphatic amines in bioactive small molecules, amine derivatives are opportune as directing groups. Herein, sulfamides serve as amine surrogates to guide intermolecular chlorine-transfer at γ-C(sp3) centers. This unusual position-selectivity arises because accessed sulfamidyl radical intermediates engage preferentially in otherwise rare 1,6-hydrogen-atom transfer (HAT) processes through seven-membered transition states. The site-selectivity of C–H abstraction can be modulated by adjusting the steric and electronic properties of the sulfamide nitrogen substituents, an ability that has not been demonstrated with other substrate classes. The disclosed reaction relies on a light-initiated radical chain-propagation mechanism to oxidize C(sp3)–H bonds efficiently.

Graphical abstract: Sulfamides direct radical-mediated chlorination of aliphatic C–H bonds

Supplementary files

Article information

Article type
Edge Article
Submitted
11 juil. 2019
Accepted
06 nov. 2019
First published
08 nov. 2019
This article is Open Access

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

Chem. Sci., 2020,11, 217-223

Sulfamides direct radical-mediated chlorination of aliphatic C–H bonds

M. A. Short, M. F. Shehata, M. A. Sanders and J. L. Roizen, Chem. Sci., 2020, 11, 217 DOI: 10.1039/C9SC03428E

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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