Catalytic intermolecular amination of C-H bonds: method development and mechanistic insights.
Reaction methodology for intermolecular C-H amination of benzylic and 3 degrees C-H bonds is described. This process uses the starting alkane as the limiting reagent, gives optically pure tetrasubstituted amines through stereospecific insertion into enantiomeric 3 degrees centers, displays high chemoselectivity for benzylic oxidation, and enables the facile preparation of isotopically enriched 15N-labeled compounds. Access to substituted amines, amino alcohols, and diamines is thereby made possible in a single transformation. Important information relevant to understanding the initial steps in the catalytic cycle, reaction chemoselectivity, the nature of the active oxidant, and pathways for catalyst inactivation has been gained through mechanistic analysis; these studies are also presented.
Fiori
Kristin Williams
KW
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
Du Bois
J
J
D000473:Alkanes / Q000737:chemistry*; D000588:Amines / Q000737:chemistry*; D000605:Amino Alcohols / Q000737:chemistry; D001555:Benzene Derivatives / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D003959:Diamines / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D009587:Nitrogen Isotopes / Q000737:chemistry; D010084:Oxidation-Reduction; D013056:Spectrophotometry, Ultraviolet
D000473:Alkanes; D000588:Amines; D000605:Amino Alcohols; D001555:Benzene Derivatives; D003959:Diamines; D009587:Nitrogen Isotopes; D002244:Carbon; D006859:Hydrogen