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

[41] Tertiary Carbinamine Synthesis by Rhodium-Catalyzed [3+2] Annulation of N-Unsubstituted Aromatic Ketimines and Alkynes
Sun, Zhong-Ming
Chen, Shuo-Ping
Zhao, Pinjing
CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (08) : 2619 - 2627
[42] Mechanistic DFT Study on Rhodium(III)-Catalyzed Double C-H Activation for Oxidative Annulations of 2-Substituted Imidazoles and Alkynes
Xie, Peipei
Jia, Mengmeng
Xu, Xiao-Hua
Chen, Fan
Xia, Yuanzhi
ASIAN JOURNAL OF ORGANIC CHEMISTRY, 2018, 7 (03) : 586 - 591
[43] Rhodium-Catalyzed C-H Activation/Annulation Cascade of Aryl Oximes and Propargyl Alcohols to Isoquinoline N-Oxides
Li, Yuan
Fang, Feifei
Zhou, Jianhui
Li, Jiyuan
Wang, Run
Liu, Hong
Zhou, Yu
ADVANCED SYNTHESIS & CATALYSIS, 2021, 363 (13) : 3305 - 3310
[44] Synthesis of Benzopyrans by Enolate-Directed Rhodium-Catalyzed Oxidative C-H Alkenylation of 1,3-Dicarbonyl Compounds
Bollikolla, Hari Babu
Choppakatla, Subrahmanyam
Polam, Naresh
Thripuram, Vijaya Durga
Chidipudi, Suresh Reddy
ASIAN JOURNAL OF ORGANIC CHEMISTRY, 2017, 6 (11) : 1598 - 1603
[45] Ruthenium(II)-Catalyzed C-H Bond [3+2] Annulation of N-Nitrosoanilines with Alkynes in Water
Chen, Xun
Cui, Xue
Bai, Lili
Wang, Ying
Xie, Ying
Wang, Shuojin
Zhai, Ruirui
Zhao, Ke
Kong, Dulin
Li, Youbin
ASIAN JOURNAL OF ORGANIC CHEMISTRY, 2019, 8 (12) : 2209 - 2212
[46] Asymmetric Synthesis of Spiropyrazolones by Rhodium-Catalyzed C(sp2)-H Functionalization/Annulation Reactions
Zheng, Jun
Wang, Shao-Bo
Zheng, Chao
You, Shu-Li
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (16) : 4540 - 4544
[47] Rhodium-Catalyzed [3+2] Annulation of Cyclic N-Acyl Ketimines with Activated Olefins: Anticancer Activity of Spiroisoindolinones
Sharma, Satyasheel
Oh, Yongguk
Mishra, Neeraj Kumar
De, Umasankar
Jo, Hyeim
Sachan, Richa
Kim, Hyung Sik
Jung, Young Hoon
Kim, In Su
JOURNAL OF ORGANIC CHEMISTRY, 2017, 82 (07) : 3359 - 3367
[48] Rhodium(III)-Catalyzed Olefinic C-H Alkynylation of Acrylamides Using Tosyl-Imide as Directing Group
Feng, Chao
Feng, Daming
Luo, Yang
Loh, Teck-Peng
ORGANIC LETTERS, 2014, 16 (22) : 5956 - 5959
[49] Rhodium-Catalyzed C-H Bond Activation/[4+2] Annulation/Aromatization Cascade To Produce Phenol, Naphthol, Phenanthrenol, and Triphenylenol Derivatives
Hojo, Daiki
Tanaka, Ken
ORGANIC LETTERS, 2012, 14 (06) : 1492 - 1495
[50] Efficient Access to Isoquinolines via Rhodium-Catalyzed Oxidative Annulation of Pyridyl C-H Bonds Directed by Carbonyl with Internal Alkynes
Shi, Lijun
Wen, Mingshan
Li, Fuwei
SYNTHESIS-STUTTGART, 2021, 53 (03): : 538 - 546

← 1 2 3 4 5 →