Organocatalytic Asymmetric Allylic Benzylborylation via Fluoride-Assisted Catalytic Generation of α-Boryl Carbanionic Intermediates

Abstract

Herein we describe the organocatalytic asymmetric allylic benzylborylation of allyl fluorides with α-silyl benzylboronic esters. The catalytic protocol leverages the singular features of fluoride as an unconventional leaving group, enabling the catalytic generation of reactive α-boryl carbanion species through desilylative activation. It allows the construction of a wide set of homoallylic benzylated organoboronates bearing two contiguous stereocenters. The chiral boronate installed in the products serves as a synthetic lynchpin to construct complex chemical architectures in a stereospecific manner.