交叉偶联反应4.pdfVIP

Organoboron Compounds Norio Miyaura Division of Molecular Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo, 060-8628, Japan E-mail: miyaura@org-mc.eng.hokudai.ac.jp Until recently, organoboronic acids had found limited use in organic synthesis due to their low reactivity for ionic reactions. However, it became increasingly clear that they are a valuable reagent capable of undergoing many catalytic carbon-carbon bond formations in organic syntheses including asymmetric synthesis, combinatorial synthesis, and polymer synthesis. A review of the metal-catalyzed cross-coupling reaction of these compounds is presented here with particular emphasis on their application in selective organic syntheses. Representative methods for achieving selective coupling are outlined, along with a survey of a wide range of C-C bond formations. Keywords. Cross-coupling reaction, Organoboron compounds, Palladium and nickel catalysts, Carbon-carbon bond formation 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 2 Catalytic Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 3 Reaction Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . 15 3.1 Catalysts, Bases, and Solvents . . . . . . . . . . . . . . . . . . . . . 15 3.1.1 Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 3.1.2 Bases and Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 3.2 Side Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 3.2.1 Participation of Phosphine-Bound Aryls . . . . . . . . . . . . . . . 24 3.2.2 Oxygen-Induced Homo