Synthetic Strategies toward Ortho-3-propanoate Substituted Aryl Phosphonates by Three-Component Coupling Reactions of Arynes, Phosphites, and Acrylates DOI
Donghwa Shin, Soomin Kim, Duck‐Hyung Lee

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 8035 - 8040

Published: May 28, 2024

Mild, metal-free, and operationally simple three-component coupling reactions involving arynes, phosphites, acrylates have been achieved. The reaction proceeded well with α- or β-substituted acrylates. Additionally, various functional groups were tolerated under these conditions, resulting in diverse

Language: Английский

Recent Advances in the Application of P(III)-Nucleophiles to Create New P−C Bonds through Michaelis–Arbuzov-Type Rearrangement DOI
Biquan Xiong,

Minjing Yuan,

Chonghao Shi

et al.

Topics in Current Chemistry, Journal Year: 2024, Volume and Issue: 382(1)

Published: March 1, 2024

Language: Английский

Citations

6
A simple method for N-arylation of secondary amides/amines through a NaH-initiated aryne generation strategy DOI

Yuanrui Jiang,

Wenjing Zhu,

Jiawen Huang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(1), P. 12 - 20

Published: Oct. 3, 2023

A very simple and practical method has been uncovered for N -arylation of many sets secondary amides/amines.

Language: Английский

Citations

10
The Reaction of Aryl Thiols or Thioureas with o‐Diiodoarenes/NaH to Access o‐Iodoaryl Thioethers DOI

Min Hu,

Dianfan Liu,

Yuan Liu

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(7), P. 1538 - 1544

Published: Feb. 8, 2024

Abstract Herein we report a method for the synthesis of thioethers by forging C(aryl)‐S bond via an aryne mechanism. The active species can be generated from o ‐diiodoarenes and NaH in THF at room temperature, then lead to arylations wide range aryl thiols thioureas. Different transition metal‐catalyzed cross‐coupling reactions, no disubstituted byproduct is formed our protocol. ‐iodoaryl thioether products are intermediates that could transformed into pharmaceutically interesting molecules.

Language: Английский

Citations

4
Synthesis of Phosphachromones by Cyclized Coupling of Ethyl Hydrogen (Phenylethynyl)phosphonate with Arynes DOI
Yu Guo,

Jianke Su,

Jian Xu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(35), P. 6459 - 6463

Published: Aug. 25, 2023

A straightforward and efficient strategy for the synthesis of phosphachromones has been reported via insertion arynes into P–O bonds. This operationally simple reaction is compatible with different functional groups, affording various by simultaneous formation C–P C–O bonds in one step moderate to good yields, Fries rearrangement involving phosphorus atoms a key reaction.

Language: Английский

Citations

6
Recent Progress on Arylation with Aryne through Three-Component Reaction DOI Open Access
Dongping Chen,

Yang Chunhong,

Ming Li

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 43(2), P. 503 - 503

Published: Jan. 1, 2023

The three component reaction has the advantages of simple operation and efficient reaction, in line with principles atomic economy green environmental protection.At present, arylation without transition metal catalyst is mainly divided into types as following: (1) direct arylation, (2) insertion aryne σ-bond or π-bond, (3) three-component reactions involving aryne.Compared mechanism still unclear, published reviews are lacking.In order to facilitate scientific researchers consult understand involved aryne, progresses recent years reviewed.

Language: Английский

Citations

5
The Aryne-Abramov Reaction as a 1,2-Benzdiyne Platform for the Generation and Solvent-Dependent Trapping of 3-Phosphonyl Benzynes DOI
Brianna M. Bembenek,

Maya M. S. Petersen,

Julia A. Lilly

et al.

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(15), P. 10724 - 10746

Published: July 8, 2021

Synthetic methodology utilizing two aryne intermediates (i.e., a formal benzdiyne) enables the rapid generation of structurally complex molecules with diverse functionality. This report describes sequential ortho-benzyne for synthesis 2,3-disubstituted aryl phosphonates. Aryl phosphonates have proven useful in medicinal chemistry and materials science, reported provides two-step route to functionally dense variants by way 3-phosphonyl benzyne intermediates. The process begins regioselective trapping 3-trifloxybenzyne intermediate an O-silyl phosphite Abramov-like reaction bond strained Csp carbons phosphorus silicon. Standard aryne-generating conditions follow convert resulting 2-silylphenyl triflate into benzyne, which readily reacts numerous reactants form variety 2,3-difunctionalized phosphonate products. DFT computational studies shed light on important mechanistic details revealed that benzynes are highly polarizable. Specifically, distortion internal angles at each atoms was strongly influenced both electronegativity ester groups as well dielectric solvation model. These effects were verified experimentally regioselectivity benzyl azide increased more electronegative esters and/or increasingly polar solvents. Conversely, replacing conventional solvent, acetonitrile, nonpolar alternatives provided attenuated or even inverted selectivities. Overall, these showcase new reactivity extend relay include organophosphonates. Furthermore, this work demonstrates reactions could be tuned simply changing solvent.

Language: Английский

Citations

11
Synthesis of Benzoxaphosphole 1-Oxide Heterocycles via a Three-Component Coupling Reaction Involving Arynes, Phosphites, and Ketones DOI

Hee Jin Jeong,

Ji Ho Kim,

Jae Kyun Lee

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(11), P. 2192 - 2196

Published: March 14, 2022

An efficient and transition-metal-free three-component reaction with benzynes formed in situ from 2-(trimethylsilyl)aryl triflate, phosphites, ketones was developed for the synthesis of benzoxaphosphole 1-oxides. array 1-oxides were prepared both activated non-activated moderate to good yields a broad functional group tolerance. This is useful preparing organophosphorus compounds encountered natural products materials.

Language: Английский

Citations

8
Fluoride-Mediated Aryne 1,2-Difunctionalization Involving C═S Bond Heterolysis DOI
Dong‐Ping Chen,

Chunhong Yang,

Wenpeng Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: July 1, 2024

We have successfully synthesized a series of bidentate ligands by utilizing 2-(trimethylsilyl)phenyl trifluorosulfonate as precursor for the benzyl group. This method proceeded inserting polythiourea into C═S π-bond, intramolecular ring proton migration, and opening. Salient features this strategy are mild reaction conditions, novel product structure, excellent stereochemistry, good functional group tolerance. Furthermore, density theory calculations were performed to gain insights transfer mechanism.

Language: Английский

Citations

1
Room-temperature synthesis of m-benzyne DOI
Kenta Koyamada, Kazunori Miyamoto, Masanobu Uchiyama

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(9), P. 1083 - 1090

Published: July 17, 2024

Language: Английский

Citations

1
Synthetic Strategy for Aryl(alkynyl)phosphinates by a Three-Component Coupling Reaction Involving Arynes, Phosphites, and Alkynes DOI

Su Hyun Ji,

Soomin Kim, Ghilsoo Nam

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(45), P. 8295 - 8299

Published: Nov. 7, 2022

An efficient and straightforward method for the synthesis of aryl(alkynyl)phosphinates was developed via a three-component coupling reaction involving arynes, phosphites, alkynes. array were produced from both aryl aliphatic group-substituted acetylenes. This operationally simple is tolerant to many functional groups, affording various in moderate good yields. The synthetic utility alkynyl phosphinates afforded by this demonstrated elaboration products into phosphorus-containing compounds.

Language: Английский

Citations

6