Synthesis of Tertiary Allylboronates from Vinylboronates

Abstract

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.

Key words

boron - homogeneous catalysis - copper - organometallic reactions - allylation

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• 14 The results of such an oxidation to yield a tertiary allylic alcohol are included in the Supporting Information. Compounds not found within the text are numbered sequentially beginning with 9.
• 15 A mechanistic rationale for E-selectivity is included in the Supporting Information.