Metal-catalyzed reactions of diborons for synthesis of organoboron compounds.

Abstract

Metal-catalyzed borylation of alkenes, alkynes, arenes, and organic halides with B-B or H-B compounds has been developed for the synthesis of organoboron compounds from simple organic substrates. The platinum(0)-catalyzed addition of bis(pinacolato)diboron to alkenes and alkynes provided a method for the stereoselective synthesis of cis-bis(boryl)alkanes or cis-bis(boryl)alkenes. The addition of diboron to 1,3-dienes with platinum(0) complexes provided a new access to cis-1,4-bis(boryl)-2-butene derivatives, which are versatile reagents for diastereoselective allylboration of carbonyl compounds. The first one-step procedure for the syntheses of aryl-, vinyl-, and allylboronates was achieved via crosscoupling reactions of diborons with aryl and 1-alkenyl halides or triflates and allyl acetates. Direct C-H borylation of arenes catalyzed by a transition metal complex was studied as an economical protocol for the synthesis of a variety of arylboron derivatives. Ir-catalyzed C-H borylation of arenes, heteroarenes, and benzylic positions of alkylarenes by bis(pinacolato)diboron or pinacolborane furnished aryl-, heteroaryl-, and benzylboron compounds. This article discusses the mechanisms of these reactions and their synthetic applications.