Unveiling the role of molecule-assisted homolysis: a mechanistic probe into the chemistry of a bicyclic peroxide.

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 alpha,beta-unsaturated keto-aldehyde, is proposed. Surprisingly, molecule-assisted homolysis plays a key role in this transformation, the details of which are discussed herein.