Silylative cyclopropanation of allyl phosphates with silylboronates

Angew Chem Int Ed Engl. 2014 Jun 16;53(25):6546-9. doi: 10.1002/anie.201403726. Epub 2014 May 13.

Abstract

A potassium-bis(trimethylsilyl)amide-mediated cyclopropanation of allyl phosphates with silylboronates has been developed. Unlike the reported copper-catalyzed allylic substitution reactions, the nucleophile selectively attacks at the β-position of the allylic substrates under the present reaction conditions. The mechanism of this process has also been investigated, thus indicating the involvement of a silylpotassium species as the active nucleophilic component.

Keywords: reaction mechanisms; rearrangement; silanes; small ring system; synthetic methods.