Mechanism, bonding nature of metal-nitrenoid, and selectivity for a nitrene-participating three-component carboamination of dienes: A DFT study

被引：7

作者：

Chu, Yichun ^{[1
]}

Bi, Siwei ^{[1
]}

Wu, Xiaohan ^{[1
]}

Jiang, YuanYe ^{[1
]}

Liu, Yuxia ^{[1
]}

Ling, Baoping ^{[1
]}

Yuan, Xiang-Ai ^{[1
]}

机构：

[1] Qufu Normal Univ, Sch Chem & Chem Engn, Qufu 273165, Shandong, Peoples R China

来源：

MOLECULAR CATALYSIS | 2020年 / 497卷

基金：

中国国家自然科学基金;

关键词：

Carboamination; Dienes; Metal nitrenoid; Selectivity; DFT calculations; C-H AMIDATION; AB-INITIO PSEUDOPOTENTIALS; AMIDO TRANSFER; N-OXIDE; AMINATION; HETEROCYCLES; ENERGIES; CARBON; MILD;

D O I：

10.1016/j.mcat.2020.111222

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A theoretical and computational study was performed on the nitrene-participating three-component carboamination of dienes. The reaction proceeds mainly through C-H activation, olefin insertion, metal nitrenoid formation, and selective C-N coupling. The role of solvent effect enables the extrusion of carbon dioxide to generate the key metal nitrenoid being not concerted but stepwise. The Rh = N was indicated by HOMO-LUMO interactions that the backdonation is dominant and hence showing the electron withdrawing behavior of nitrene. Regioselectivity for C-C bond formation, E-type product, and 1,4-carboamination was discussed.

引用

页数：7

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