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
收藏
页码：4494 / 4503
页数：10
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