论文部分内容阅读
合成了手性氨基酸衍生的苯并咪唑和二肽衍生的苯并咪唑配体.手性氨基酸衍生的苯并咪唑2与[RuCl_2(p-cymene)]2原位生成的催化剂在苯乙酮的不对称氢转移反应中表现出较好的催化性能,反应的转化速率(TOF)可以达到15400 h-1,产物的对映体选择性达到77%.通过构效关系的研究认为,金属钌与配体可能是通过吡咯烷上的NH和离子化的酰胺部分的N配位.通过动力学计算解释了[RuCl_2(p-cymene)]_2/2在苯乙酮的氢转移反应中表现出的反常温度效应.在二肽衍生的苯并咪唑配体7与[RuCl_2(p-cymene)]2原位生成的催化体系中加入添加剂Li Cl,可以使产物的对映体选择性由38%提高到43%.
Synthesis of chiral amino acid-derived benzimidazole and dipeptide-derived benzimidazole ligands Chiral amino acid-derived benzimidazole 2 and [RuCl_2 (p-cymene)] 2 in situ generated catalyst in the acetophenone Asymmetric hydrogen transfer reaction showed good catalytic performance, the reaction conversion rate (TOF) can reach 15400 h-1, the product of the enantioselectivity of 77% .Study on the structure-activity relationship that the metal ruthenium and The ligand may be due to the N coordination of the NH group on the pyrrolidine and the amide part of the ionization.The kinetic calculation of [RuCl 2 (p-cymene)] _ 2/2 in the hydrogen transfer reaction of acetophenone Anomalous temperature effect: The addition of LiCl to the catalytic system in situ generated by dipeptide-derived benzimidazole ligand 7 and [RuCl_2 (p-cymene)] 2 increased the enantioselectivity of the product from 38% To 43%.