铱-氮膦配体催化剂在非官能化烯烃不对称氢化中的研究

Asymmetric Hydrogenation of Unfunctionalized Alkenes Catalyzed by Ir-N,P-Ligand Catalysts

非官能化烯烃的不对称氢化反应一直是烯烃加氢领域的难点。研究表明,铱-氮膦配体催化剂对此类反应具有很好的催化活性和选择性,因而受到国内外众多学者的关注。本文对近年来利用铱-氮膦配体催化剂对非官能化烯烃进行不对称氢化的研究进展进行了综述,介绍了不对称氢化的发展历程及背景,着重讨论了铱-氮膦配体催化剂的催化机理(IrⅢ-IrⅤ催化循环机理、IrⅠ-IrⅢ催化循环机理)、铱催化剂的组成以及催化性能的比较,并对铱催化剂在不对称氢化中的发展前景作了展望。

The asymmetric hydrogenation of unfunctionalized alkenes which the carbon-carbon double bonds are connected only to totally aliphatic groups is always a challenge in the field of alkene hydrogenation. It is reported that such reaction can be catalyzed by Ir-N, P-ligand catalysts with excellent catalytic activity and high enantioselectivity, which deserves much attention over the world. In the present review, the progress on asymmetric hydrogenation of unfunctionalized alkenes catalyzed by Ir-N, P-ligand catalysts are described, including the background of thehydrogenation history, the catalytic mechanisms （Ir^Ⅲ-Ir^Ⅴ cycle mechanism and Ir^Ⅰ-Ir^Ⅲ cycle mechanism）, the composition of the catalysts （the precursors of Ir catalysts, the chiral ligands and the anions） and the comparison of their reactivity while catalyzing olefins with di-, tri- and tetra- substituted alkyl groups. The prospective of the asymmetric hydrogenation of unfunctionalized alkenes by Ir-N, P-ligand catalysts is also presented.