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新型手性配体的设计合成是不对称催化研究的重要内容,其中手性胺膦配体因同时含有“软”的磷原子和“硬”的氮原子而具有丰富的配位化学性能和优秀的不对称诱导能力.本文总结了本研究组最近设计合成的手性环状胺膦配体的制备、表征及其在铁催化酮的不对称还原中的应用.手性1,2-环己二胺与双(2-甲酰基苯基)苯基膦通过[2+2]环缩合反应能够顺利获得手性22元环的亚胺膦配体21,该配体经Na BH4还原后生成大环胺膦配体22.利用手性大环胺膦配体22与Fe3(CO)12原位生成的催化体系,能够高活性、高对映选择性地实现包括杂环芳香酮在内50多种酮的不对称转移氢化和不对称氢化反应,其S/C(底物与催化剂的摩尔比)最高可达5000:1,产物手性芳香醇的光学纯度高达99%ee.
The design and synthesis of novel chiral ligands are an important part of the asymmetric catalysis, in which the chiral phosphine ligands are abundantly coordinated by both a “soft” phosphorus atom and a “hard” nitrogen atom Chemical properties and excellent asymmetric induction ability.This paper summarizes the recent design and synthesis of the group of chiral cyclic amine phosphine ligand preparation and characterization and its application in the iron catalyzed asymmetric reduction of ketones.Chiral 1, 2-Cyclohexanediamine and bis (2-formylphenyl) phenylphosphine can be successfully obtained through the [2 + 2] ring condensation reaction. The 22-ring chiral iminophosphine ligand 21 can be successfully obtained by Na BH4 After reduction, the macrocyclic aminophosphine ligands 22 are formed.Using the catalytic system formed in situ by the chiral macrocyclic aminophosphine ligands 22 and Fe3 (CO) 12, high activity and high enantioselectivity can be achieved including heterocyclic aromatic ketones Asymmetric transfer hydrogenation and asymmetric hydrogenation of more than 50 ketones, the S / C (molar ratio of substrate to catalyst) is up to 5000: 1, and the optical purity of the product chiral aromatic alcohol is up to 99% ee.