Issue 1, 2018

Site-selective bromination of sp3 C–H bonds


A method for converting sp3 C–H to C–Br bonds using an N-methyl sulfamate directing group is described. The reaction employs Rh2(oct)4 and a mixture of NaBr and NaOCl and is performed in aqueous solution open to air. For all sulfamates examined, oxidation occurs with high selectivity at the γ-carbon, affording a uniquely predictable method for C–H bond halogenation. Results from a series of mechanistic experiments suggest that substrate oxidation likely proceeds by a radical chain process. Initial formation of an N-halogenated sulfamate followed by Rh-mediated homolysis generates an N-centered radical, which serves as the active oxidant.

Graphical abstract: Site-selective bromination of sp3 C–H bonds

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Article information

Article type
Edge Article
25 Oct 2017
18 Nov 2017
First published
20 Nov 2017
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., 2018,9, 100-104

Site-selective bromination of sp3 C–H bonds

S. Sathyamoorthi, S. Banerjee, J. Du Bois, N. Z. Burns and R. N. Zare, Chem. Sci., 2018, 9, 100 DOI: 10.1039/C7SC04611A

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