Theoretical study on the intramolecular oxyamination involved in Rh(III)-catalyzed cyclization of unsaturated alkoxyamines

被引：3

作者：

Bi, Siwei ^{[1
]}

Wang, Yueyue ^{[1
]}

Jiang, Yuan-Ye ^{[1
]}

Liu, Yuxia ^{[1
]}

机构：

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

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2019年 / 880卷

基金：

中国国家自然科学基金;

关键词：

Intramolecular oxyamination; Rh(III)-catalysis; Unsaturated alkoxyamine; Nitrene Rh(V) species; DFT calculation; EFFECTIVE CORE POTENTIALS; MOLECULAR CALCULATIONS; DENSITY FUNCTIONALS; AMINOHYDROXYLATION; ACTIVATION;

D O I：

10.1016/j.jorganchem.2018.11.019

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The unexpected oxyamination reaction of O, omega-unsaturated alkoxyamines was found experimentally. The mechanistic issues were studied by DFT calculations. It is suggested that the reaction undergoes [3 + 2] cyclic addition, O-N bond cleavage, C-N reductive elimination, and the Rh-N unit protonation, generating the product and regenerating the active catalyst. The nitrene Rh(V) species containing a Rh-C bond rather than a Rh-O bond was suggested to be involved in the reaction mechanism. Why the substrate A with X = O but not X = C undergoes oxyamination reaction was rationalized based on the suggested reaction mechanism. (c) 2018 Elsevier B.V. All rights reserved.

引用

页码：253 / 260

页数：8

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