Ligand-Substrate Dispersion Facilitates the Copper-Catalyzed Hydroamination of Unactivated Olefins was written by Lu, Gang;Liu, Richard Y.;Yang, Yang;Fang, Cheng;Lambrecht, Daniel S.;Buchwald, Stephen L.;Liu, Peng. And the article was included in Journal of the American Chemical Society in 2017.Category: chiral-phosphine-ligands This article mentions the following:
The current understanding of ligand effects in transition metal catalysis is mostly based on the anal. of catalyst-substrate through-bond and through-space interactions, with the latter commonly considered to be repulsive in nature. The dispersion interaction between the ligand and the substrate, a ubiquitous type of attractive noncovalent interaction, is seldom accounted for in the context of transition-metal-catalyzed transformations. Herein we report a computational model to quant. analyze the effects of different types of catalyst-substrate interactions on reactivity. Using this model, we show that in the copper(I) hydride (CuH)-catalyzed hydroamination of unactivated olefins, the substantially enhanced reactivity of copper catalysts based on bulky bidentate phosphine ligands originates from the attractive ligand-substrate dispersion interaction. These computational findings are validated by kinetic studies across a range of hydroamination reactions using structurally diverse phosphine ligands, revealing the critical role of bulky P-aryl groups in facilitating this process. In the experiment, the researchers used many compounds, for example, (R)-(-)-2,2′-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-6,6′-dimethoxy-1,1′-biphenyl (cas: 352655-61-9Category: chiral-phosphine-ligands).
(R)-(-)-2,2′-Bis[di(3,5-di-t-butyl-4-methoxyphenyl)phosphino]-6,6′-dimethoxy-1,1′-biphenyl (cas: 352655-61-9) belongs to chiral phosphine ligands. At present, the synthesis of new chiral phosphines designed specifically for nucleophilic organocatalysis remains a significant challenge. Effective chiral catalysts for nucleophilic phosphine catalysis are scarce, seriously limiting the development of asymmetric variants. Category: chiral-phosphine-ligands
Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis