Highly Stereoselective Syntheses of α,α-Disubstituted (E)- and (Z)‑Crotylboronates

We report herein stereoselective syntheses of α,α-disubstituted (E)- and (Z)-crotylboronates. Starting from α-boryl (E)- or (Z)-crotylboronate, base-mediated alkylation occurred exclusively at the position α to the boryl groups to give targeted boronates while retaining the geometries of the alkenes in the starting crotylboronates. Under proper conditions, the resulting α,α-disubstituted crotylboronates underwent aldehyde addition to give allylated products with high stereoselectivities.