Homologation of Electron-Rich Benzyl Bromide Derivatives via Diazo C-C Bond Insertion

The ability to manipulate C-C bonds for selective chemical transformations is challenging and represents a growing area of research. Here, we report a formal insertion of diazo compounds into the unactivated C-C bond of benzyl bromide derivatives catalyzed by a simple Lewis acid. The homologation reaction proceeds via the intermediacy of a phenonium ion, and the products contain benzylic quaternary centers and an allcyl bromide amenable to further derivatization. Computational analysis provides critical insight into the reaction mechanism, in particular the key selectivity-determining step.

Automated summary

The ability to manipulate C-C bonds for selective chemical transformations is a challenging and growing area of research. The study reported a formal insertion of diazo compounds into unactivated C-C bonds of benzyl bromide derivatives catalyzed by a simple Lewis acid, resulting in products containing benzylic quaternary centers and alkyl bromides amenable to further derivatization. Computational analysis provided insight into the reaction mechanism, particularly the key selectivity-determining step.