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
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
Publication Date (Web): May 30, 2013
Address (URL): http://pubs.acs.org/doi/abs/10.1021/jo400944r