Synthesis of Highly Congested Tertiary Alcohols via the [3,3] Radical Deconstruction of Breslow Intermediates

Pericyclic processes such as [3,3]-sigmatropic rearrangements leading to the rapid generation of molecular complexity constitute highly valuable tools in organic synthesis. Herein, we report the formation of particularly hindered tertiary alcohols via rearrangement of Breslow intermediates formed in situ from readily available N-allyl thiazolium salts and benzaldehyde derivatives. Experimental mechanistic studies performed suggest that the reaction proceeds via a close radical pair which recombine in a regioand diastereoselective manner, formally leading to [3,3]-rearranged products.

Automated summary

This study reports a method for synthesizing particularly hindered tertiary alcohols via rearrangement reactions using [3,3]-sigmatropic rearrangements. Experimental studies suggest that the reaction proceeds through a close radical pair, leading to highly selective rearranged products.