Site-selective bromination of sp3 C–H bonds

Shyam Sathyamoorthi; Shibdas Banerjee; J. Du Bois; Noah Z. Burns; Richard N. Zare

doi:10.1039/C7SC04611A

Site-selective bromination of sp³ C–H bonds†

Shyam Sathyamoorthi,

^a Shibdas Banerjee,^b J. Du Bois,*^a Noah Z. Burns

*^a and Richard N. Zare

*^a

Author affiliations

* Corresponding authors

^a Stanford University, Department of Chemistry, 333 Campus Drive, Stanford, CA 94305-4401, USA
E-mail: zare@stanford.edu, jdubois@stanford.edu, nburns@stanford.edu

^b Indian Institute of Science Education and Research Tirupati, Karakambadi Road, Tirupati-517507, India

Abstract

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.

This article is part of the themed collection: 2018 International Open Access Week Collection

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Article information

DOI: https://doi.org/10.1039/C7SC04611A
Article type: Edge Article
Submitted: 25 Oct 2017
Accepted: 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

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Chem. Sci., 2018,9, 100-104

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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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