Mechanistic Insights Into the Rhodium-Catalyzed C-H Alkenylation/ Directing Group Migration and [3+2] Annulation: A DFT Study

被引：0

作者：

Ling, Baoping ^{[1
]}

Wang, Shuangjie ^{[1
]}

Xie, Yuxin ^{[1
]}

Liu, Peng ^{[1
]}

Jiang, Yuan-Ye ^{[1
]}

Zhong, Wenhui ^{[1
]}

Bi, Siwei ^{[1
]}

机构：

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

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2023年 / 88卷 / 07期

基金：

中国国家自然科学基金;

关键词：

AB-INITIO PSEUDOPOTENTIALS; TETRASUBSTITUTED ALKENES; DENSITY FUNCTIONALS; PROPARGYL ALCOHOLS; M06; SUITE; ALKYNES; BENZAMIDES; ELEMENTS; INDOLES;

D O I：

10.1021/acs.joc.2c03089

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The mechanism of the rhodium-catalyzed C-H alkenylation/directing group migration and [3+2] annulation of N- aminocarbonylindoles with 1,3-diynes has been investigated with DFT calculations. On the basis of mechanistic studies, we mainly focus on the regioselectivity of 1,3-diyne inserting into the Rh-C bond and the N-aminocarbonyl directing group migration involved in the reactions. Our theoretical study uncovers that the directing group migration undergoes a stepwise beta-N elimination and isocyanate reinsertion process. As studied in this work, this finding is also applicable to other relevant reactions. Additionally, the role of Na+ versus Cs+ involved in the [3+2] cyclization reaction is also probed.

引用

页码：4494 / 4503

页数：10

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