Fu Gregory C
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, USA.
Acc Chem Res. 2008 Nov 18;41(11):1555-64. doi: 10.1021/ar800148f.
Metal-catalyzed coupling reactions of aryl electrophiles with organometallics and with olefins serve as unusually effective tools for forming new carbon-carbon bonds. By 1998, researchers had developed catalysts that achieved reactions of aryl iodides, bromides, and triflates. Nevertheless, many noteworthy challenges remained; among them were couplings of aryl iodides, bromides, and triflates under mild conditions (at room temperature, for example), couplings of hindered reaction partners, and couplings of inexpensive aryl chlorides. This Account highlights some of the progress that has been made in our laboratory over the past decade, largely through the appropriate choice of ligand, in achieving these synthetic objectives. In particular, we have established that palladium in combination with a bulky trialkylphosphine accomplishes a broad spectrum of coupling processes, including Suzuki, Stille, Negishi, and Heck reactions. These methods have been applied in a wide array of settings, such as natural-product synthesis, materials science, and bioorganic chemistry.
芳基亲电试剂与有机金属化合物以及与烯烃的金属催化偶联反应是形成新碳-碳键极为有效的工具。到1998年，研究人员已开发出能实现芳基碘化物、溴化物和三氟甲磺酸酯反应的催化剂。然而，许多值得关注的挑战依然存在；其中包括在温和条件下（例如室温）芳基碘化物、溴化物和三氟甲磺酸酯的偶联反应、受阻反应底物的偶联反应以及廉价芳基氯化物的偶联反应。本综述重点介绍了我们实验室在过去十年中，主要通过合理选择配体，在实现这些合成目标方面所取得的一些进展。特别是，我们已经证实钯与大位阻三烷基膦结合可实现广泛的偶联反应，包括铃木反应、施蒂勒反应、根岸反应和赫克反应。这些方法已应用于众多领域，如天然产物合成、材料科学和生物有机化学。
