title: Unveiling the role of molecule-assisted homolysis: a mechanistic probe into the chemistry of a bicyclic peroxide.
abstract: Unlike the reaction of aryl-substituted diazenes, pyrolysis of alkyl-substituted diazenes in the presence of molecular oxygen generates an unexpectedly complex product mixture. Using deuterium labeling studies, in conjunction with quantum calculations, a reasonable mechanistic hypothesis for the decomposition of the resultant [3.3.0] peroxide, and subsequent formation of the keto-alcohol and Z-configured α,β-unsaturated keto-aldehyde, is proposed. Surprisingly, molecule-assisted homolysis plays a key role in this transformation, the details of which are discussed herein.
authors.affiliation: Department of Chemistry and Biochemistry, University of California at Santa Barbara, Santa Barbara, California 93106, USA.
authors.forename: Randi K
authors.initials: RK
authors.lastname: Gbur
authors.forename: R Daniel
authors.initials: RD
authors.lastname: Little
mesh_terms: D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010545:Peroxides / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D001643:Bridged Bicyclo Compounds; D010545:Peroxides