Heui Beom Lee - Fine-Tuning the Oxidative Ability of Persistent Radicals: Electrochemical and Computational Studies of Substituted 2-Pyridylhydroxylamines

Version 1

      Publication Details (including relevant citation   information):

        Justin A. Bogart, Heui Beom Lee, Michael A. Boreen, Minsik Jun,   and Eric J. Schelter

        P. Roy and Diana T. Vagelos Laboratories, Department of   Chemistry,   University of Pennsylvania,   231 South 34th Street, Philadelphia, Pennsylvania 19104, United   States

      Abstract:

        N-tert-Butyl-N-2-pyridylhydroxylamines   were synthesized from 2-halopyridines and   2-methyl-2-nitrosopropane using magnesium–halogen exchange. The   use of Turbo Grignard generated the metallo-2-pyridyl   intermediate more reliably than alkyllithium reagents. The   hydroxylamines were characterized using NMR, electrochemistry,   and density functional theory. Substitution of the pyridyl ring   in the 3-, 4-, and 5-positions was used to vary the potential of   the nitroxyl/oxoammonium redox couple by 0.95 V. DFT computations   of the electrochemical properties agree with experiment and   provide a toolset for the predictive design of pyridyl   nitroxides.

      J. Org. Chem., 2013, 78 (12), pp 6344–6349

    DOI: 10.1021/jo400944r

    Publication Date (Web): May 30, 2013

      Address (URL): http://pubs.acs.org/doi/abs/10.1021/jo400944r