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C−Boron Enolates Enable Palladium Catalyzed Carboboration of Internal 1,3‐Enynes

Ziyong Wang, Jason Wu, Walid Lamine, Bo Li, Jean‐Marc Sotiropoulos, Anna Chrostowska, Karinne Miqueu, Shih‐Yuan Liu

2021Angewandte Chemie International Edition32 citationsDOIOpen Access PDF

Abstract

Abstract A 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 Pd 0 /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.

Topics & Concepts

AlkyneNucleophileBoronChemistryCatalysisEnyneLigand (biochemistry)ElectrophileHalogenMedicinal chemistryCombinatorial chemistryOrganic chemistryReceptorBiochemistryAlkylOrganoboron and organosilicon chemistryCatalytic Cross-Coupling ReactionsCatalytic C–H Functionalization Methods