钴催化的偶联 综述.pdfVIP

Pure Appl. Chem., Vol. 78, No. 2, pp. 441–449, 2006. doi:10.1351/pac200678020441 © 2006 IUPAC New synthetic reactions catalyzed by cobalt complexes* Hideki Yorimitsu and Koichiro Oshima‡ Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto-daigaku Katsura, Nishikyo-ku, 615-8510 Kyoto, Japan Abstract : Without suffering from β-elimination, cobalt complexes allow cross-coupling re- actions of alkyl halides with Grignard reagents. A combination of a cobalt complex and trimethylsilylmethyl Grignard reagent effects Mizoroki–Heck-type reaction of alkyl halide with styrene, which conventional palladium catalysts have never made possible. Cobalt ex- hibits intriguing catalytic activities on hydrophosphination and allylzincation of alkynes. Silylmethylcobalt reagent is a powerful tool for the synthesis of highly silylated ethenes. Keywords: cobalt; synthesis; Grignard reagents; cross-coupling reactions; Mizoroki–Heck re- actions. INTRODUCTION Palladium and nickel catalysts play a key role in modern organic synthesis. Cross-coupling and Mizoroki–Heck reactions are among the most important carbon–carbon bond-formation reactions. Normally, aryl and vinyl halides are the choice of the substrates, since the use of alkyl halides having hydrogen at the β-position to the halide atom suffers from β-hydride elimination unless intensive screening of reaction conditions was performed. During the course of our study on transition-metal-cat- alyzed reaction [1], readily available cobalt complexes were found to act as catalysts complementary to palladium and nickel in cross-coupling and Mizoroki–Heck reactions. The cobalt-catalyzed reactions probably proceed via carbon-centered radicals as key intermediates that are gen