手性磷-烯配体在不对称催化领域的研究进展  

Chiral Phosphorus-Olefin Ligands for Asymmetric Catalysis

作　　者：于月娜 徐明华[1] Yu Yue-Na Xu Ming-Hua(State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203, China)

机构地区：[1]中国科学院上海药物研究所新药研究国家重点实验室,上海201203

出　　处：《化学学报》2017年第7期655-670,共16页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.21325209;21472205);上海市优秀学术带头人计划(No.14XD1404400)资助~~

摘　　要：手性磷-烯配体在不对称催化反应中的应用近年来受到化学家们的关注,已经成为一个热门的研究领域.磷-烯配体作为一类新兴杂化烯烃配体,将具有强配位能力的磷原子与配位方式特殊但配位能力相对较弱的碳-碳双键结合在一起,兼具了部分手性膦配体和手性双烯配体的优点,在一些过渡金属如铑、钯、铱等催化的不对称反应中表现出独特的催化性能,不但能高效催化反应,而且能取得优异的对映选择性.本文综述了自2004年首例磷-烯配体的合成及应用报道以来该领域的研究进展,对过去十几年中发展的各种手性磷-烯配体的结构特征、合成方法以及它们在不同催化不对称反应中的应用进行了分类概括,期望为未来进一步拓展手性烯烃配体的类型和应用提供思考和方向.Transition-metal-catalyzed asymmetric transformations are among the most powerful and straightforward strate- gies to access various enantioenriched compounds. Hence, considerable efforts have been focused on the development of novel chiral ligands capable of highly effcient and enantioselective catalysis. The importance of olefin as ligand in transi- tion-metal-catalyzed reactions wasn＇t realized until the report of the Zeise＇ salt in 1827. Nevertheless, application of chiral olefins as ligands for asymmetric catalysis has been overlooked for quite a long time owing to their relatively weak binding affinity toward the central metal. Since the groundbreaking work of Hayashi and Carreira in 2003-2004, chiral dienes as steering ligands in asymmetric catalysis have emerged as a fascinating new feld. Given the weak coordination ability of olefins to transition-metals, functional groups with high coordination ability were considered to incorporate into the olefin framework to create a new type of hybrid olefin ligands for asymmetric catalysis. Over the past few years, a diverse range of hybrid olefn ligands were developed for various enantioselective transformations. Among these, phosphorus-based otefins represent a particularly interesting class of ligands since the first concept demonstration by Gr^tzmacher in 2004, combining the strong coordinating phosphorus atom and the weak coordinating olefin into one ligand molecule. Typically, three structur- ally different types of phosphorus-based olefins are known in the literature, including phosphine-olefins, phospho- ramidite/phosphinamidite-olefins, and phosphite/phosphinite-olefins. They have been successfully utilized in a series of tran- sition-metal-catalyzed asymmetric reactions, such as iridium-catalyzed asymmetric hydrogenation of imines, allylic substitu- tion; rhodium-catalyzed conjugate addition of organoboron reagents to α,β-unsaturated compounds, 1,2-addition of organo- boron reagents to imines/carbonyl compounds, intramolecular hydroacylation; and pa

关 键 词：不对称催化 手性配体 烯烃配体 磷-烯配体 不对称合成 

分 类 号：O641.4[理学—物理化学] O643.36[理学—化学]