Revealing Dinitrogen Activation via Mesoionic Carbenes: A Computational Design with Frustrated Lewis Pairs DOI
Shiqing Huang, Tian Wang, Zengyu Zhang

et al.

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

Published: Nov. 13, 2024

Abstract Activating dinitrogen under metal‐free conditions remains a significant challenge in chemistry. In this study, we computationally designed frustrated Lewis pair (FLP) system incorporating bis(trimethylsilyl)boryl substituent on mesoionic carbene (MIC) framework. Our models show both kinetic and thermodynamic favorability for activation. Aromaticity enhancement along the potential energy surface (PES) plays critical role driving reaction. This work provides insights into utilizing main‐group elements activation offers applications inert molecule optical materials.

Language: Английский

Benzothiazolines Acting as Carbanion and Radical Transfer Reagents in Carbon–Carbon Bond Construction DOI Creative Commons
Xiaotang Chen,

Bao‐Chen Qian

Molecules, Journal Year: 2025, Volume and Issue: 30(8), P. 1711 - 1711

Published: April 11, 2025

Traditionally employed as hydrogenation reagents, benzothiazolines have emerged versatile carbanion and radical transfer playing a vital role in the construction of various carbon-carbon bonds. The cutting-edge progress photochemistry chemistry prompted study visible light-driven reactions, bringing into vibrant focus. Their chemical processes been uncovered to encompass variety activation mechanisms, with five distinct modes having identified. This work reviews innovative applications donors alkyl or acyl groups, achieving hydroalkylation hydroacylation substitution. By examining their diverse this review highlights potential serving groups for further research development. Moreover, will offer exemplary inspiration synthetic chemists, contributing ongoing evolution utility organic synthesis.

Language: Английский

Citations

0
Switching Mesoionic Carbene-Organocatalysis from Radical to Ionic Pathway through Base-Controlled Formation of Breslow Intermediates versus Breslow Enolates DOI Creative Commons
J. B. Jiao, Zengyu Zhang,

Guangyin Lu

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

N-heterocyclic carbene (NHC) organocatalysis has experienced significant advancements. Two distinct reaction pathways have been developed, ionic and radical, through Breslow intermediates (BIs) enolates (BI-s), respectively. The ability to selectively generate these is crucial for optimizing outcomes. In this paper we show that with mesoionic carbenes (MICs) it possible control the formation of BIs versus BI-s, use weak bases strong bases, Of particular interest coupling aldehydes alkyl halides yield ketones via an pathway.

Language: Английский

Citations

0
Construction of C–S and C–Se Bonds via Photocatalytic Aromatization-Driven Deconstructive Diversification of Spiro-Dihydroquinazolinones Derived from Unstrained Ketones DOI
Tao Wang,

Jin‐Long Dai,

Yifeng Jiang

et al.

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

Published: May 13, 2025

A novel and robust deconstructive functionalization reaction of spiro-dihydroquinazolinones with sulfenylating reagents in the presence base has been realized under visible light irradiation. This enabled direct ring-opening unstrained cyclic ring systems, producing skeletally diverse functionalized quinazolinones moderate to good yields. range variety including diaryl disulfide, thiosulfonate, dithiosulfonate 1-[(trifluoromethyl)thio]-2,5-pyrrolidinedione were compatible for this transformation. In addition, diselenide selenosulfonate could also couple form C-Se Bonds. Mechanistic studies revealed that proceeds via a radical-radical coupling pathway.

Language: Английский

Citations

0
Redox-Paired Reductive Heck Reaction and Oxidative Esterification Catalyzed by Mesoionic Carbenes DOI

B. HUANG,

Zengyu Zhang, J. B. Jiao

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(35), P. 7419 - 7424

Published: Aug. 22, 2024

Paring a reductive reaction and an oxidative in one could be immensely important achieving atom economic environmental advantages. Herein, we report simple protocol that combines two such Heck reactions esterification by using mesoionic carbenes as catalysts to synthesize multiple valuable products under mild conditions.

Language: Английский

Citations

3
Cooperative Photoredox and N-Heterocyclic Carbene-Catalyzed Formal C-H Acylation of Cyclopropanes via Deconstruction-Reconstruction Strategy DOI Creative Commons
Fan Gao,

Tian Wang,

Xiaoyu Yan

et al.

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

Published: Jan. 1, 2024

Cooperative NHC/photoredox catalyzed deconstruction–reconstruction of aryl cyclopropanes was described to access various α-acylated cyclopropane derivatives.

Language: Английский

Citations

2
Ketone Skeletal Modification via a Metallaphotoredox-Catalyzed Deacylation and Acylation Strategy DOI

Ke‐Han He,

Na Jin, J. Paul Chen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(44), P. 9503 - 9507

Published: Oct. 28, 2024

Herein, we describe a dual catalytic strategy that employs dihydroquinazolinones, derived from ketone analogs, as versatile intermediates for acylation via α C–C cleavage with 2-pyridyl esters, facilitating the efficient synthesis of variety ketones. The reaction accommodates wide range ketones and carboxylic acids, showing tolerance to various functional groups. versatility this synthetic technique is further highlighted through its application in late-stage modification pharmaceuticals biologically active natural products.

Language: Английский

Citations

1
Electrochemical C H alkylation of N-heterocycles via aromatization-driven C C fragmentation of unstrained ketones DOI
Peng Ye, Yi Xiong, Bo Zhang

et al.

Tetrahedron Letters, Journal Year: 2024, Volume and Issue: 155, P. 155440 - 155440

Published: Dec. 27, 2024

Language: Английский

Citations

1
Deuteration Degree Controllable Synthesis of Aryl Deuteromethyl Ethers Through Dual photoredox and Thiol Catalysis DOI
Junjie Yang, Zhongxian Li,

Zhihui Huang

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(62)

Published: Aug. 22, 2024

Herein, we report a facile and efficient deuteration degree controllable method for the preparation of aryl deuteromethyl ethers through dual photoredox thiol catalysis using phenols as starting materials inexpensive D

Language: Английский

Citations

0
Photoredox decarboxylative acylation of carboxylic acid by 4-acyl-1,2,3-triazoliums DOI Creative Commons
Zengyu Zhang, Shiqing Huang, Fan Gao

et al.

Green Synthesis and Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 1, 2024

Language: Английский

Citations

0
Revealing Dinitrogen Activation via Mesoionic Carbenes: A Computational Design with Frustrated Lewis Pairs DOI
Shiqing Huang, Tian Wang, Zengyu Zhang

et al.

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

Published: Nov. 13, 2024

Abstract Activating dinitrogen under metal‐free conditions remains a significant challenge in chemistry. In this study, we computationally designed frustrated Lewis pair (FLP) system incorporating bis(trimethylsilyl)boryl substituent on mesoionic carbene (MIC) framework. Our models show both kinetic and thermodynamic favorability for activation. Aromaticity enhancement along the potential energy surface (PES) plays critical role driving reaction. This work provides insights into utilizing main‐group elements activation offers applications inert molecule optical materials.

Language: Английский

Citations

0