Late‐stage Functionalization using a Popular Titrating Agent: Aryl‐Chlorides and ‐Fluorides Activation by the Diphenylacetic Acid Dianion DOI Creative Commons

Alessandro Cerveri,

Giulia Russo, Sara Sparascio

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 31(8)

Published: Oct. 27, 2024

Abstract Aryl‐chlorides and ‐fluorides are common building blocks, but their use in synthesis is limited by the high stability of Ar−X bonds. The generation aryl radicals via activation strong bonds possible through irradiation tailor‐made organic anions, which become reductants stronger than lithium metal. We report that combination visible light with cheap diphenylacetic acid dianion an even better tool, showing excellent activity across a variety complex substrates providing opportunities for late‐stage drug modification. chemoselectively activated presence more easily reducible functions, such as Alk‐Cl ones carbonyl groups. These results pave way to original synthetic strategies would be otherwise considered impossible.

Language: Английский

Electro-reductive carboxylation of C Cl bonds in unactivated alkyl chlorides and polyvinyl chloride with CO2 DOI
Li Li, Zhi-xin Yan,

Chuan‐Kun Ran

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(12), P. 110104 - 110104

Published: June 8, 2024

Language: Английский

Citations

9
Photoinduced N-heterocyclic nitrenium-catalyzed single electron reduction of Se–Se bond for the generation of nucleophilic selenolates DOI
Chaoshen Zhang,

Kun‐Quan Chen,

Ling Zhou

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(7), P. 2070 - 2074

Published: Jan. 1, 2024

A straightforward photoinduced NHN-catalyzed method for generating nucleophilic selenolates from diselenides without the need of stoichiometric reductants.

Language: Английский

Citations

4
Construction of axially chiral molecules enabled by photoinduced enantioselective reactions DOI Creative Commons
Zhaofei Zhang, Lei Dai

Chemical Science, Journal Year: 2024, Volume and Issue: 15(32), P. 12636 - 12643

Published: Jan. 1, 2024

Axially chiral molecular scaffolds are widely found in pharmaceutical molecules, functionalized materials, and ligands. The synthesis of these compounds has garnered considerable interest from both academia industry. construction such enabled by transition metal catalysis organocatalysis under thermodynamic conditions, been extensively studied well-reviewed. In recent years, photoinduced enantioselective reactions have emerged as powerful methods for the catalytic axial chirality. this review, we provide an overview various synthetic strategies chirality, with a specific focus on reaction design mechanisms. Additionally, discuss limitations current highlight future directions field.

Language: Английский

Citations

4
Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp3)–C(sp3) Bond Formation DOI Creative Commons

Chang-Zhen Fang,

Beibei Zhang,

Yongliang Tu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 12, 2024

The ligated boryl radical (LBR) has emerged as a potent tool for activating alkyl halides in transformations through halogen-atom transfer (XAT). However, unactivated chlorides still present an open challenge this strategy. We herein describe new activation mode of the LBR to construct C(sp

Language: Английский

Citations

4
Co-Catalytic Coupling of Alkyl Halides and Alkenes: the Curious Role of Lutidine DOI Creative Commons

Roshini Hanumanthu,

Parul Sharma,

Avery Ethridge

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 2, 2025

Continuous pressure to shorten synthetic sequences along with the concomitant expansion of scope makes use alkyl bromides, chlorides, and oxygen based leaving groups- which are abundant readily available feedstocks, highly attractive for C-C bond synthesis. However, selective activation these bonds generate radical intermediates remains challenging is generally unfeasible using traditional strategies. Herein, we report a dual catalytic strategy access primary, secondary, tertiary radicals from respective chlorides as well primary tosylates trifluoroacetates. While method relies on visible light photocatalyst facilitate electron transfer, reduction potentials, substrates not expected be reduceable, yet they reduced in presence lutidine. Ultimately, our investigation revealed that lutidine was precatalyst ultimately led lutidinium iodide salt served critical cocatalyst resulted improved reaction profiles. Our studies two roles salts play made it possible engage otherwise unreactive substrates: nucleophilic exchange halogen atom transfer by radical. In short, this work converts unactivated tosylates, trifluoroacetates can used formation without need preactivation─effectively expediting

Language: Английский

Citations

0
Photoinduced N‑Heterocyclic Nitrenium-Catalyzed Single Electron Reduction of α-Chloro Esters for Phenanthridine Synthesis DOI
Ling Zhou,

Xue‐Feng Pei,

Wei Gong

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

An efficient photoactive charge transfer complex protocol for the synthesis of phenanthridine derivatives by reaction 2-isocyanobiaryls with α-chloro esters is established.

Language: Английский

Citations

0
N‐Heterocyclic Carbene/Transition Metal Dual Catalysis DOI
Zhaofei Zhang, Chunlin Zhang,

Song Ye

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 17, 2024

Abstract N‐heterocyclic carbene catalysis has been developed as a versatile method for the enantioselective synthesis of complex organic molecules in chemistry. Merging with transition metal holds potential to achieve unprecedented transformations broad substrate scope and excellent stereoselectivity, which are unfeasible individual catalyst. Thus, this dual attracted increasing attention, numerous elegant catalytic systems have established. In review, we summarize recent achievements NHC/transition catalysis, including reaction design, mechanistic studies practical applications.

Language: Английский

Citations

3
Photoinduced Single Electron Reduction of the 4‐O‐5 Linkage in Lignin Models for C‐P Coupling Catalyzed by Bifunctional N‐Heterocyclic Carbenes DOI Creative Commons
Qiang Liu,

Ying‐Zheng Ren,

Bei‐Bei Zhang

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(38)

Published: Aug. 5, 2024

Abstract Catalytic activation of C aryl ‐O bonds is considered as a powerful strategy for the production aromatics from lignin. However, due to high reduction potentials diaryl ether 4‐O‐5 linkage models, their single electron remains daunting challenge. This study presents blue light‐induced bifunctional N‐heterocyclic carbene (NHC)‐catalyzed one‐electron models synthesis trivalent phosphines. The H‐bond between newly devised NHC and ethers responsible success transfer. Furthermore, this approach demonstrates selective unsymmetric ethers, oligomeric phenylene oxide, lignin model.

Language: Английский

Citations

3
Trinuclear gold-catalyzed site-selective alkylation of peptides DOI

Qing-Yun Fang,

Chengyihan Gu,

Yinghan Chen

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 14, 2024

Language: Английский

Citations

2
Late‐stage Functionalization using a Popular Titrating Agent: Aryl‐Chlorides and ‐Fluorides Activation by the Diphenylacetic Acid Dianion DOI Creative Commons

Alessandro Cerveri,

Giulia Russo, Sara Sparascio

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 31(8)

Published: Oct. 27, 2024

Abstract Aryl‐chlorides and ‐fluorides are common building blocks, but their use in synthesis is limited by the high stability of Ar−X bonds. The generation aryl radicals via activation strong bonds possible through irradiation tailor‐made organic anions, which become reductants stronger than lithium metal. We report that combination visible light with cheap diphenylacetic acid dianion an even better tool, showing excellent activity across a variety complex substrates providing opportunities for late‐stage drug modification. chemoselectively activated presence more easily reducible functions, such as Alk‐Cl ones carbonyl groups. These results pave way to original synthetic strategies would be otherwise considered impossible.

Language: Английский

Citations

1