摘要
过渡金属络合物催化的烯烃的氢化和硅氢化反应是两类非常重要和基础的催化有机合成转化,在工业生产中广泛应用。[1]目前这两类反应所用的催化剂主要是基于铑、钌、铱、铂等贵金属,存在资源稀缺、价格昂贵、具有生物毒性等问题,不符合绿色化学和可持续化学发展的要求。铁是地壳中含量最高的过渡金属,也是最便宜的金属,具有良好的生物兼容性,被认为是理想的过渡金属催化剂。目前使用,铁代替贵金属催化烯烃的氢化和硅氢化反应是催化有机合成领域研究的热点和前沿,同时存在巨大挑战。我们从铁负氢活性物种的生成和氢转移的角度出发,发展了从稳定的铁络合物现场合成活性铁催化剂的新方法,并以此为基础,通过配体设计,发现了目前用于烯烃催化氢化的最高效铁络合物催化剂,并首次实现了铁催化烯烃的马氏加成硅氢化反应。[2]
Transition-metal-catalyzed hydrogenation and hydrosilylation of olefins are among the most important organic transformations.The most popular catalysts for hydrogenation and hydrosilylation reactions are based on precious metals,such as rhodium,ruthenium,iridium,and platinum.The exhausting resource,the increasing high price,and the toxicity of the above mentioned metals restrict their future applications.Iron is the most abundant transition metal in the Earth crust and therefor cheapest one with excellent environmental benign characters,and has been considered as the ideal potential catalyst for hydrogenation reactions but still with significant challenges at present.Herein we reported the recent development of iron-catalyzed hydrogenation and hydrosilylation of olefins from thehydrogen transfer perspective in our laboratory.
引文
[1](a)de Vries,J.G.;Elsevier,C.J.(Eds).The Handbook of Homogeneous Hydrogenation,Wiley-VCH:Weinheim,2007.(b)Hydrosilylation,A Comprehensive Review on Recent Advances,Marciniec,B.(Ed.)Spring,2009.
[2](a)Guo,N.;Hu,M.-Y.;Feng,Y.;Zhu,S.-F.Org.Chem.Front.2015,2,692.(b)Hu,M.-Y.;He,Q.;Liu,L.-Y.;Wang,Z.-W.;Mu,Y.-J.;Zhu,S.-F.Submitted.