title: A General Catalyst for Site-Selective C(sp(3))-H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp(3))-H Bonds.
abstract: The discovery of transition metal complexes capable of promoting general, catalyst-controlled and selective carbon-hydrogen (C-H) bond amination of activated secondary C-H bonds over tertiary alkyl C(sp(3))-H bonds is challenging, as substrate control often dominates when reactive nitrene intermediates are involved. In this letter, we report the design of a new silver complex, [(Py5Me2)AgOTf]2, that displays general and good-to-excellent selectivity for nitrene insertion into propargylic, benzylic, and allylic C-H bonds over tertiary alkyl C(sp(3))-H bonds.
authors.affiliation: Department of Chemistry, University of Wisconsin , Madison, Wisconsin 53706, United States.
authors.forename: Ryan J
authors.initials: RJ
authors.lastname: Scamp
authors.affiliation: Department of Chemistry, University of Wisconsin , Madison, Wisconsin 53706, United States.
authors.forename: James G
authors.initials: JG
authors.lastname: Jirak
authors.affiliation: Department of Chemistry, University of Wisconsin , Madison, Wisconsin 53706, United States.
authors.forename: Nicholas S
authors.initials: NS
authors.lastname: Dolan
authors.affiliation: Department of Chemistry, University of Wisconsin , Madison, Wisconsin 53706, United States.
authors.forename: Ilia A
authors.initials: IA
authors.lastname: Guzei
authors.affiliation: Department of Chemistry, University of Wisconsin , Madison, Wisconsin 53706, United States.
authors.forename: Jennifer M
authors.initials: JM
authors.lastname: Schomaker
mesh_terms: D000475:Alkenes / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry; D000586:Amination; D001593:Benzyl Compounds / Q000737:chemistry; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry*; D006860:Hydrogen Bonding; D007097:Imines / Q000737:chemistry*; D012834:Silver / Q000737:chemistry*
chemical_list: D000475:Alkenes; D000480:Alkynes; D001593:Benzyl Compounds; D056831:Coordination Complexes; D007097:Imines; C017621:phenylnitrene; D012834:Silver