Combination of transition metal Rh-catalysis and tautomeric catalysis through a bi-functional ligand for one-pot tandem methoxycarbonylation-aminolysis of olefins towards primary amides
作者:Peng Wang、Lei Liu、Zhoujie Luo、Qing Zhou、Yong Lu、Fei Xia、Ye Liu
DOI:10.1016/j.jcat.2018.03.003
日期:2018.5
catalysis has been emerged as a powerful strategy to promote organic transformations that cannot be achieved by each individual independently. Herein, a new protocol for the synthesis of primary amides from olefins, CO and NH3 through one-pot tandem methoxycarbonylation-aminolys was presented over a bi-functional ligand (L1) based rhodium catalyst with functions of co-catalysis. L1 is composed of the phosphino-fragment
过渡金属催化与有机催化以协同催化,协同催化或/和顺序催化的方式相结合已成为一种强有力的策略,可以促进每个人无法独立实现的有机转化。在此,在具有共催化功能的基于双功能配体(L1)的铑催化剂上,提出了一种通过一锅串连的甲氧基羰基化-氨基分解物从烯烃,CO和NH 3合成伯酰胺的新方案。L1由膦片段和氨基/亚氨基互变异构部分组成。然后L1的Rh催化体系证明了Rh-P过渡金属催化和互变异构催化的结合。在这种串联的甲氧基羰基化-氨解反应中,NH 3还用作配体,与膦酸酯片段协同作用,共同修饰负责烯烃第一步甲氧基羰基化以生成酯的Rh催化剂的性能,并且Rh-tailed互变异构体催化剂负责随后的氨解反应以生成目标伯酰胺。