Metal-Catalyzed Reactions of Organoboronic Acids and Esters

• Published in: Bulletin of the Chemical Society of Japan Vol. 81; no. 12; pp. 1535 - 1553
• Main Author: Miyaura, Norio
• Format: Journal Article
• Language: English
• Published: Tokyo The Chemical Society of Japan 15.12.2008; Chemical Society of Japan
• Series: The Chemical Society of Japan Award for 2007
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.81.1535

Metal-catalyzed B–C and C–C bond-forming reactions of organoboronic acids that have been pursued in the past three decades by our group are summarized in this article. B–C bond-forming reactions for the synthesis of organoboronic acid derivatives include metal-catalyzed addition reactions of pinacolborane or catecholborane (hydroboration), bis(pinacolato)diboron (diboration), and alkylthioboranes (thioboration) to alkenes, alkynes, 1,3-alkadienes, or 1,2-alkadienes (allenes). Other B–C bond-forming reactions include coupling reactions of pinacolborane or bis(pinacolato)diboron for borylation of C–halogen bonds with palladium catalysts and C–H bonds of arenes and alkenes with iridium catalysts. These reactions have provided a convenient new access to aryl-, 1-alkenyl-, allyl-, or benzylboronates. Metal-catalyzed C–C and C–N bond-forming reactions using boronic acid derivatives include synthesis of novel cyclic triolborate salts for palladium- or copper-catalyzed cross-coupling reactions with organic halides or amines, rhodium- or palladium-catalyzed 1,4-addition reactions of arylboronic acids to α,β-unsaturated carbonyl compounds and rhodium-catalyzed addition of aryl- and 1-alkenylboronic acids to aldehydes and imines.