The Thermal Reaction of Sterically Hindered Nitroxyl Radicals with Allylic and Benzylic Substrates:  Experimental and Computational Evidence for Divergent Mechanisms

• Published in: Journal of organic chemistry Vol. 67; no. 19; pp. 6831 - 6834
• Main Authors: Babiarz, Joseph E, Cunkle, Glen T, DeBellis, Anthony D, Eveland, David, Pastor, Stephen D, Shum, Sai P
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 20.09.2002; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Exact sciences and technology; Kinetics and mechanisms; Organic chemistry; Physical Sciences; Reactivity and mechanisms; Science & Technology; ATOMIC-HYDROGEN; ALKENES; POLYMERIZATIONS; AUTOPOLYMERIZATION; RELEVANCE; Nitroxyl; Nitrogen heterocycle; Theoretical study; Steric hindrance; Thermal reaction; Experimental study; Allylic compound; Amine; Benzylic compound; Cyclic compound; Organic free radical; Piperidine derivatives; Reaction mechanism; Chemical synthesis; Ethylenic compound
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo020426r

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.