The thermal reaction of sterically hindered nitroxyl radicals with allylic and benzylic substrates: experimental and computational evidence for divergent mechanisms.
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.
Babiarz
Joseph E
JE
Ciba Specialty Chemicals Corporation, 540 White Plains Road, P.O. Box 2005, Tarrytown, New York 10591, USA.
Cunkle
Glen T
GT
DeBellis
Anthony D
AD
Eveland
David
D
Pastor
Stephen D
SD
Shum
Sai P
SP