Abstract

AbstractOrganoboron compounds, especially alkenylboronates and arylboronates are highly useful reagents and versatile building blocks in the modern synthetic chemistry toolbox. This review focuses on copper‐catalyzed routes to access alkenyl‐ and arylboronate esters. Various copper salts and ligands have been employed to access them in excellent regio‐ and stereoselectivity as well as high yields. Both addition and substitution reactions to alkenylboronates have been highlighted based on various methodologies including hydroboration, carboboration, borylative opening of propargyl three‐ and four‐membered rings, dehalogenative borylation of alkenyl bromides and iodides, defluoroborylation of fluoroalkenes and direct C(sp2)−H bond activation of alkenes. Preparation of arylboronates involving borylation of aryl halides, C(sp2)−H borylation of arenes and cascade 1,3‐halogen migration/borylation of 2‐halostyrenes have been reviewed. Mechanistic aspects of those borylation reactions are discussed briefly.

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