(Z)-α-Boryl-crotylboron reagents via Z-selective alkene isomerization and application to stereoselective syntheses of (E)-δ-boryl-syn-homoallylic alcohols

Stereoselective synthesis of (Z)-α-boryl-crotylboronate is developed. Ni-catalyzed Z-selective alkene isomerization of α-boryl substituted homoallylboronate provided the targeted (Z)-crotylboronate with high selectivity. Stereoselective addition of the novel crotylboron reagent to aldehydes gave (E)-δ-boryl-substituted syn-homoallylic alcohols with excellent diastereoselectivities. The vinyl boronate unit in the products can be directly used for a subsequent C–C bond-forming transformation as illustrated in the synthesis of the C(1–7) fragment of the natural products nannocystin A and nannocystin Ax.