Isayama–Mukaiyama Peroxidation Eschews Ozonolysis in Hydrodealkenylation

Advancements in radical capture strategies have expanded the range of products accessible from alkenes through dealkenylative synthesis. These methods, however, are still limited, as they rely on ozonolysis to generate the key peroxide intermediates from alkenes. Ozonolysis has specific limitations: it is incompatible with alkenes containing electronrich aromatics, unproductive alkene substitution patterns, sterically hindered alkenes, internal nucleophiles and electrophiles, and allylic alcohols. In this paper, using Isayama–Mukaiyama peroxidation (IMP), we address the limitations of ozonolysis to rescue previously inaccessible alkene substrates and broaden the applicability of dealkenylative functionalization. In addition, we describe a novel reductive hydrogenation—employing catalytic [FeIII], catalytic benzenethiol, and γ-terpinene in refluxing methanol—to resolve β-scission issues associated with IMP-generated alkyl silylperoxides.