Abstract

AbstractA new family of carbon‐bound boron enolates, generated by a kinetically controlled halogen exchange between chlorocatecholborane and silylketene acetals, is described. These C−boron enolates are demonstrated to activate 1,3‐enyne substrates in the presence of a Pd0/Senphos ligand complex, resulting in the first examples of a carboboration reaction of an alkyne with enolate‐equivalent nucleophiles. Highly substituted dienyl boron building blocks are produced in excellent site‐, regio‐, and diastereoselectivity by the described catalytic cis‐carboboration reaction.

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