title: Catalyst-Controlled and Tunable, Chemoselective Silver-Catalyzed Intermolecular Nitrene Transfer: Experimental and Computational Studies.
abstract: The development of new catalysts for selective nitrene transfer is a continuing area of interest. In particular, the ability to control the chemoselectivity of intermolecular reactions in the presence of multiple reactive sites has been a long-standing challenge in the field. In this paper, we demonstrate examples of silver-catalyzed, nondirected, intermolecular nitrene transfer reactions that are both chemoselective and flexible for aziridination or C-H insertion, depending on the choice of ligand. Experimental probes present a puzzling picture of the mechanistic details of the pathways mediated by [(tBu3tpy)AgOTf]2and (tpa)AgOTf. Computational studies elucidate these subtleties and provide guidance for the future development of new catalysts exhibiting improved tunability in group transfer reactions.
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: Ryan J
authors.initials: RJ
authors.lastname: Scamp
authors.affiliation: Department of Chemistry, University of Wisconsin , Madison, Wisconsin 53706, United States.
authors.forename: Tzuhsiung
authors.initials: T
authors.lastname: Yang
authors.affiliation: Department of Chemistry, University of Wisconsin , Madison, Wisconsin 53706, United States.
authors.forename: John F
authors.initials: JF
authors.lastname: Berry
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: D000586:Amination; D002384:Catalysis; D003198:Computer Simulation; D007097:Imines / Q000737:chemistry*; D007536:Isomerism; D015394:Molecular Structure; D012834:Silver / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D007097:Imines; C017621:phenylnitrene; D012834:Silver