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

Published

Journal Article

© 2019 The Royal Society of Chemistry. 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.

Full Text

Duke Authors

Cited Authors

  • Short, MA; Shehata, MF; Sanders, MA; Roizen, JL

Published Date

  • January 1, 2020

Published In

Volume / Issue

  • 11 / 1

Start / End Page

  • 217 - 223

Electronic International Standard Serial Number (EISSN)

  • 2041-6539

International Standard Serial Number (ISSN)

  • 2041-6520

Digital Object Identifier (DOI)

  • 10.1039/c9sc03428e

Citation Source

  • Scopus