Synthesis of Tertiary Allylboronates from Vinylboronates

Allylic boronates are versatile intermediates in organic synthesis. Herein, we present an ‘ate-mediated allylic substitution’ (AMAS) approach to allylic boronates. Bifunctional vinylboroate/ allylic acetate esters react with Grignard reagents to form tertiary ­allylic boronates via an AMAS reaction. We demonstrate that the method tolerates a wide range of substrates and Grignard reagents.