Unveiling the role of molecule-assisted homolysis: a mechanistic probe into the chemistry of a bicyclic peroxide |
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Authors: | Gbur Randi K Little R Daniel |
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Affiliation: | Department of Chemistry and Biochemistry, University of California at Santa Barbara, Santa Barbara, California 93106, USA. |
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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. |
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