Hansen Jørn, Davies Huw M L
Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York, 14260-3000.
Coord Chem Rev. 2008 Mar;252(5-7):545-555. doi: 10.1016/j.ccr.2007.08.019.
The design and use of chiral dirhodium(II) paddlewheel complexes as catalysts for asymmetric metal carbenoid and metal nitrenoid reactions, and as Lewis acids have become areas of considerable interest during the past two decades. The metal carbenoid chemistry is especially versatile, encompassing transformations such as C-H insertions, cyclopropanations and ylide formation. A number of different classes of dirhodium(II) catalysts have been found to be broadly effective in this chemistry. This review will highlight that many of these catalysts have higher symmetry than the individual chiral ligands themselves. An introduction of theoretical aspects concerning the structure and symmetry of chiral dirhodium(II) complexes will be given followed by an overview of the major classes of catalysts developed to date. Some representative examples of the synthetic potential of these catalysts will also be discussed.
在过去二十年中，手性二铑（II）桨轮配合物作为不对称金属卡宾和金属氮宾反应的催化剂以及作为路易斯酸的设计和应用已成为相当受关注的领域。金属卡宾化学特别通用，涵盖诸如C-H插入、环丙烷化和叶立德形成等转化反应。已发现许多不同类别的二铑（II）催化剂在该化学领域中具有广泛的有效性。本综述将强调这些催化剂中的许多具有比单个手性配体本身更高的对称性。将介绍有关手性二铑（II）配合物的结构和对称性的理论方面，随后概述迄今为止开发的主要催化剂类别。还将讨论这些催化剂合成潜力的一些代表性实例。
