Intermolecular C(sp3 )-H Amination of Complex Molecules

  • Angew Chem Int Ed Engl. 2018 Apr 23;57(18):4956-4959. doi: 10.1002/anie.201713225.
Nicholas D Chiappini  1 ,  James B C Mack  1 ,  J Du Bois  1
Affiliations
  • 1. Department of Chemistry, Stanford University, Stanford, CA, 94305-5080, USA.
PMID: 29484792 DOI: 10.1002/anie.201713225
Abstract

A general and operationally convenient method for intermolecular amination of C(sp3 )-H bonds is described. This technology allows for efficient functionalization of complex molecules, including numerous pharmaceutical targets. The combination of pivalonitrile as a solvent, Al2 O3 as an additive, and phenyl sulfamate as a nitrogen source affords differential reaction performance and substrate scope. Mechanistic data strongly implicate a pathway for catalyst decomposition that initiates with solvent oxidation, thus providing rationale for the marked influence of pivalonitrile on this reaction process.

Keywords
C−H oxidation; amination; reaction mechanisms; rhodium; sulfamates.
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