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

共 50 条

[31] Rhodium-catalyzed intramolecular annulation via C-H activation leading to fused tricyclic indole scaffolds
Tao, Pengyu
Jia, Yanxing
CHEMICAL COMMUNICATIONS, 2014, 50 (55) : 7367 - 7370
[32] Rhodium-Catalyzed Amination and Annulation of Arenes with Anthranils: C-H Activation Assisted by Weakly Coordinating Amides
Wang, Manman
Kong, Lingheng
Wang, Fen
Li, Xingwei
ADVANCED SYNTHESIS & CATALYSIS, 2017, 359 (24) : 4411 - 4416
[33] Ruthenium- and Rhodium-Catalyzed Dehydrogenative ortho-Alkenylation of Benzylamines via Free Amino Group Directed C-H Bond Cleavage
Suzuki, Chiharu
Morimoto, Keisuke
Hirano, Koji
Satoh, Tetsuya
Miura, Masahiro
ADVANCED SYNTHESIS & CATALYSIS, 2014, 356 (07) : 1521 - 1526
[34] Rhodium-Catalyzed Dual C-H Activation for Regioselective Triple Annulation of Enaminones: Access to Polycyclic Naphthopyran Derivatives
Suresh, Vavilapalli
Kumar, Muniganti Naveen
Nagireddy, Attunuri
Reddy, Maddi Sridhar
ADVANCED SYNTHESIS & CATALYSIS, 2023, 365 (11) : 1770 - 1776
[35] N-Sulfonylcarboxamide as an Oxidizing Directing Group for Ruthenium-Catalyzed C-H Activation/Annulation
Petrova, Elina
Rasina, Dace
Jirgensons, Aigars
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2017, 2017 (13) : 1773 - 1779
[36] DFT Mechanistic Study of Rh(III)-Catalyzed [3+2]/[5+2] Annulation of 4-Aryl-1,2,3-triazoles and Alkynes Unveils the Dual C-H Activation Strategy
Zhang, Zhongchao
Yang, Shengwen
Li, Juan
Liao, Xiaojian
JOURNAL OF ORGANIC CHEMISTRY, 2016, 81 (20) : 9639 - 9646
[37] Mechanism of Rhodium(III)-Catalyzed C-H Activation/Annulation of Aromatic Amide with α-Allenol: A Computational Study
Tian, Ruixue
Li, Yan
Liang, Changhai
JOURNAL OF ORGANIC CHEMISTRY, 2019, 84 (05) : 2642 - 2651
[38] Dienylation of Unfunctionalized Arenes with 1,6-Diynes via Rhodium-Catalyzed Directing-Group-Free C-H Bond Activation
Takahashi, Hiroto
Honjo, Yusaku
Shibata, Yu
Nagashima, Yuki
Tanaka, Ken
SYNTHESIS-STUTTGART, 2021, 53 (17): : 3065 - 3074
[39] Rhodium(III)-Catalyzed C-H Olefination for the Synthesis of ortho-Alkenyl Phenols Using an Oxidizing Directing Group
Shen, Yangyang
Liu, Guixia
Zhou, Zhi
Lu, Xiyan
ORGANIC LETTERS, 2013, 15 (13) : 3366 - 3369
[40] Synthesis of Indenones through Rhodium(III)-catalyzed [3+2] Annulation Utilizing a Recyclable Carbazolyl Leaving Group
Ochiai, Shiho
Sakai, Asumi
Usuki, Yoshinosuke
Kang, Bubwoong
Shinada, Tetsuro
Satoh, Tetsuya
CHEMISTRY LETTERS, 2021, 50 (04) : 585 - 588

← 1 2 3 4 5 →