Main Group-Catalyzed Cationic Claisen Rearrangements via Vinyl Carbocations

Org Lett. 2024 Jun 14;26(23):4847-4852. doi: 10.1021/acs.orglett.4c00837. Epub 2024 Jun 6.

Abstract

We report a catalytic C-O coupling/Claisen cascade reaction enabled by interception of vinyl carbocations with allyl ethers. The reaction utilizes commercially available borate salts as catalysts and is effective at constructing sterically hindered C-C bonds. The reaction mechanism is studied experimentally and computationally to support a charge-accelerated [3,3] rearrangement of a silyloxonium cation. Our reaction is also applied to the highly stereoselective synthesis of fully substituted vinyl ethers.