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. © 2004 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 3: 271–280; 2004: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.10068

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