Intermolecular C(sp 3 )-H Amination of Complex Molecules.

Authors :: Chiappini ND
Mack JBC
Du Bois J
Source :: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2018 Apr 23; Vol. 57 (18), pp. 4956-4959. Date of Electronic Publication: 2018 Mar 22.
Publication Year :: 2018
Abstract: A general and operationally convenient method for intermolecular amination of C(sp <superscript>3</superscript> )-H bonds is described. This technology allows for efficient functionalization of complex molecules, including numerous pharmaceutical targets. The combination of pivalonitrile as a solvent, Al <subscript>2</subscript> O <subscript>3</subscript> 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.<br /> (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)