title: The thermal reaction of sterically hindered nitroxyl radicals with allylic and benzylic substrates: experimental and computational evidence for divergent mechanisms.
abstract: The reaction of stable sterically hindered nitroxyl radicals with benzylic and allylic substrates was investigated. An allyloxyamine derivative was obtained by the reaction of 2 molar equiv of a nitroxyl radical with an unactivated alkene. Experimental and computational evidence is consistent with a low-energy pathway involving addition of the nitroxyl radical to the double bond followed by H-atom abstraction from the intermediate by another equivalent of nitroxyl radical.
authors.affiliation: Ciba Specialty Chemicals Corporation, 540 White Plains Road, P.O. Box 2005, Tarrytown, New York 10591, USA.
authors.forename: Joseph E
authors.initials: JE
authors.lastname: Babiarz
authors.forename: Glen T
authors.initials: GT
authors.lastname: Cunkle
authors.forename: Anthony D
authors.initials: AD
authors.lastname: DeBellis
authors.forename: David
authors.initials: D
authors.lastname: Eveland
authors.forename: Stephen D
authors.initials: SD
authors.lastname: Pastor
authors.forename: Sai P
authors.initials: SP
authors.lastname: Shum