Theoretical Investigation of Cp*CO(III)-Mediated Regioselective [4 + 2]-Annulation of N-Chlorobenzamide with Vinyl Acetate for the Synthesis of Isoquinolone DOI Open Access
Nan Lu, Chengxia Miao, Xiaozheng Lan

et al.

Heterocycles, Journal Year: 2023, Volume and Issue: 106(8), P. 1385 - 1385

Published: Jan. 1, 2023

The mechanism is investigated for regioselective [4 + 2]-annulation of N-chlorobenzamide catalyzed by Cp*Co(III).The CoCp*(OAc)2-mediated ortho-cobaltation via acetate-aided N-H and C-H deprotonation furnishes a five-membered intermediate, which coordinative inserted into alkene giving seven-membered cobaltacycle.The reductive elimination oxidative addition CoCp*(I) species afford six-membered ring.The recovery CoCp*(III) assisted one AcOH vinyl acetate with OAc group available to cleavage as ligand.Two ligands are both supplied ketone COMe difficult break.The acetate-assisted tautomerization produces isoquinolin-1(2H)-one.The 3-acetylisoquinolin-1(2H)-one given dehydrooxidation.The promotion Cp*Co(III) lies in the barrier decrease most steps especially deprotonation.AcOH functions protonation Cl, N sources CoCp*(III).These results supported Multiwfn analysis on FMO specific TSs MBO value vital bonding, breaking.As common heterocyclic skeletons, isoquinolones present various natural products pharmaceuticals.Their derivatives exhibit broad medicinal properties, including antitumor, antiobesity, antiviral, other effects. 1,2Hence, development practical efficient synthetic protocol construction their analogues continuous need chemists.4][5] In recent years, some novel protocols have constantly emerged such Rh(III)-catalyzed 1385

Language: Английский

Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents DOI Creative Commons
Akira Yoshimura, Viktor V. Zhdankin

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Language: Английский

Citations

34
Rhodium(III)‐Catalyzed Divergent C−H Functionalization of N‐Aryl Amidines with Iodonium Ylides: Access to Carbazolones and Zwitterionic Salts DOI
Jie Ren, Yang Liu, Chao Pi

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(11), P. 1817 - 1823

Published: Feb. 7, 2023

Abstract We described an Rhodium(III)‐catalyzed divergent C−H bond functionalization of N ‐aryl amidines with iodonium ylides. Carbazolones and zwitterionic salts were diversely constructed through intermolecular annulation intramolecular proton transfer under the different reaction conditions. This protocol is operationally simple tolerates a variety functional groups. The efficient post‐modification pharmaceutical molecules demonstrates its practicability.

Language: Английский

Citations

21
Three-Component Chemo-Selective Synthesis of N-(o-Alkenylaryl) Pyrazoles by Pyrazole Annulation and Rh-Catalyzed Chemo-Selective Aryl C–H Addition Cascade DOI

Demao Chen,

Liyun Zhou,

Chengping Wen

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(13), P. 8619 - 8627

Published: May 31, 2023

By using readily available enaminones, aryl hydrazine hydrochlorides, and alkynes as starting materials, the chemo-selective three-component synthesis of atropisomeric N-(o-alkenylaryl) pyrazoles has been efficiently accessed with rhodium catalysis. Unlike Satoh-Miura reaction leading to alkyne-based C-H benzannulation by prior prepared N-phenyl substrates, this protocol displays unprecedented selectivity alkenylation blocking second round metal key protonation step in presence acids.

Language: Английский

Citations

20
Synthesis of CF3–Isoquinolinones and Imidazole-Fused CF3–Isoquinolinones Based on C–H Activation-Initiated Cascade Reactions of 2-Aryloxazolines DOI

Miaomiao Liang,

Shengnan Yan,

Yuanshuang Xu

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(14), P. 10180 - 10196

Published: July 4, 2024

Presented herein are novel syntheses of CF

Language: Английский

Citations

9
Application of Sulfoxonium Ylides or Iodonium Ylides in Rhodium‐Catalyzed Synthesis of Phenanthrenes DOI
Xiao Liu, Bingxin Zhou, Kelu Yan

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1744 - 1750

Published: Feb. 22, 2024

Abstract The transmetalation triggered rhodium‐catalyzed C−H bond activation and tandem annulation of 2‐biphenylboronic acids with sulfoxonium ylides or iodonium has been developed. Various products phenanthrenes were constructed under redox‐neutral conditions in 34–86% yields. Several mechanism exploration experiments derivatization reactions conducted sequence to gain a deeper understanding the process potential this transformation. It offers an alternative approach for synthesis phenanthrene derivatives.

Language: Английский

Citations

6
Photoredox-Enabled Deconstructive [5 + 1] Annulation Approach to Isoquinolones from Indanones in Water DOI

Yuanyuan Fu,

Hui Liang,

Yanju Lu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3043 - 3047

Published: April 5, 2024

We disclose a deconstructive [5 + 1] annulation protocol for the synthesis of isoquinolones through nitrogen insertion into abundant indanones. This method exploits photoredox-catalyzed ring-opening oxime esters. The reaction proceeds smoothly with water as medium and tolerates range functional groups on diverse thiophenols, amines, or Moreover, representative exhibit promising antifungal activities.

Language: Английский

Citations

3
Base-Promoted Annulation of o-(Cyanomethyl)aryl Thioester with Thiophenols to Access 3-Thiolated Isoquinolones DOI

Yuanyuan Fu,

Hui Liang,

F. Li

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

An efficient annulation approach to forming 3-thiolated isoquinolones from readily accessible o-(cyanomethyl)aryl thioesters and thiophenols has been established. This metal-free is achieved by taking advantage of solvent-free reactions with no precaution exclude water or air, enabling broad substrate scope good functionality tolerance. Furthermore, the protocol scalable offers facile access valuable without chromatography.

Language: Английский

Citations

0
Iridium(III)-Catalyzed Cyclization of Oximes with Iodonium Ylides: Synthesis of Multisubstituted Heterocyclic N-Oxides DOI

N. Aravindan,

Masilamani Jeganmohan

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 29, 2025

Iridium(III)-catalyzed regioselective cyclization of substituted oximes with iodonium ylides has been described. This methodology offered multisubstituted heterocyclic N-oxides under mild reaction conditions in a redox-neutral manner. The was also compatible vinyl oximes. Additionally, substrate diversification carried out to illustrate the synthetic application protocol. A possible mechanism involving C-H bond activation proposed as well supported by isolation key five-membered iridacycle intermediate.

Language: Английский

Citations

0
Transition-Metal-Catalyzed Directed C–H Bond Functionalization with Iodonium Ylides: A Review of the Last 5 Years DOI Creative Commons

Juting Liao,

Dulin Kong,

Xiaoyang Gao

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(15), P. 3567 - 3567

Published: July 29, 2024

Transition-metal-catalyzed directed C-H functionalization with various carbene precursors has been widely employed for constructing a wide range of complex and diverse active molecules through metal migratory insertion processes. Among precursors, iodonium ylides serve as novel emerging precursor features including easy accessibility, thermal stability high activity, which have attracted great attention from organic chemists achieved tremendous success in transformation. In this review, recent progress on the application multifunctional coupling characteristics bond activation reactions is summarized, potential discussed.

Language: Английский

Citations

2
Redox-Neutral Three-Component Coupling of Phenacyl Azides, Aldehydes, and 1,3-Dicarbonyls to Access β-Enaminodiones DOI
Lodsna Borkotoky,

Uma Devi Newar,

Bipul Sarma

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(9), P. 5329 - 5340

Published: April 20, 2023

Heating an equimolar mixture of phenacyl azides, aldehydes, and cyclic 1,3-dicarbonyls to 100 °C without any solvent, catalyst, or additive led efficient three-component redox-neutral coupling yield β-enaminodiones in high yields (75-86%). The scope the synthetic method that gives dinitrogen water as only byproducts was successfully demonstrated by synthesizing 34 structurally diverse taking differentially substituted aldehydes 4-hydroxycoumarins, 4-hydroxy-1-methylquinolin-2(1H)-one dimedone.

Language: Английский

Citations

3