Hydrodealkenylative C(sp3)–C(sp2) Bond Fragmentation Using Isayama–Mukaiyama Peroxidation

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 several limitations. It is not compatible with alkenes containing electron-rich aromatics. It is also inapplicable to certain alkene substitution patterns in the context of dealkenylative synthesis. Additionally, it struggles with 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 particular, we apply IMP in hydrodealkenylation and describe a novel radical hydrogenation condition─employing catalytic [FeIII], catalytic benzenethiol, and γ-terpinene in refluxing methanol─to resolve β-scission issues associated with IMP-generated alkyl silylperoxides.