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Site-selective bromination of sp3 C–H bonds

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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.

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

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Publication details

The article was received on 25 Oct 2017, accepted on 18 Nov 2017 and first published on 20 Nov 2017


Article type: Edge Article
DOI: 10.1039/C7SC04611A
Citation: Chem. Sci., 2018, Advance Article
  • Open access: Creative Commons BY license
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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, Advance Article , DOI: 10.1039/C7SC04611A

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