Regioselective 1,2-Di(hetero)arylation of Activated and Unactivated Alkenes with (Hetero)aryl Chlorides DOI

Yingjun Lan,

Siqi Xie, Bin Liu

et al.

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

Published: May 1, 2025

Aryl chlorides are more commercially available and lower cost compared with aryl bromides iodides. However, the use of (hetero)aryl as radical precursors for di(hetero)arylation alkenes remains an underdeveloped area. Furthermore, existing examples theses reactions predominantly confined to activated alkenes. In this study, we introduce a photoirradiation-promoted benzophenone-catalyzed 1,2-di(hetero)arylation process that is applicable both unactivated alkenes, utilizing cyanoarenes sources. Importantly, method allows simultaneous introduction two heterocycles high regioselectivity.

Language: Английский

Electroreductive Cross‐Electrophile Coupling (eXEC) Reactions DOI
Yaowen Liu, Pengfei Li, Yanwei Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: June 16, 2023

Abstract Electrochemistry utilizes electrons as a potent, controllable, and traceless alternative to chemical oxidants or reductants, typically offers more sustainable option for achieving selective organic synthesis. Recently, the merger of electrochemistry with readily available electrophiles has been recognized viable increasingly popular methodology efficiently constructing challenging C−C C‐heteroatom bonds in manner complex molecules. In this mini‐review, we have systematically summarized most recent advances electroreductive cross‐electrophile coupling (eXEC) reactions during last decade. Our focus on electrophiles, including aryl alkyl (pseudo)halides, well small molecules such CO 2 , SO D O.

Language: Английский

Citations

86

Organo‐Mediator Enabled Electrochemical Deuteration of Styrenes DOI

Keming Yang,

Tian Feng, Youai Qiu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 12, 2023

Despite widespread use of the deuterium isotope effect, selective labeling chemical molecules remains a major challenge. Herein, facile and general electrochemically driven, organic mediator enabled deuteration styrenes with oxide (D2 O) as economical source was reported. Importantly, this transformation could be suitable for various electron rich mediated by triphenylphosphine (TPP). The reaction proceeded under mild conditions without transition-metal catalysts, affording desired products in good yields excellent D-incorporation (D-inc, up to >99 %). Mechanistic investigations means experiments cyclic voltammetry tests provided sufficient support transformation. Notably, method proved powerful tool late-stage biorelevant compounds.

Language: Английский

Citations

49

Alkene Hydrobenzylation by a Single Catalyst That Mediates Iterative Outer-Sphere Steps DOI

Lingran Kong,

Xu-cheng Gan, Vincent A. van der Puyl

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2351 - 2357

Published: Jan. 17, 2024

Cross-coupling catalysts typically react and unite functionally distinct partners via sequential inner-sphere elementary steps: coordination, migratory insertion, reductive elimination, etc. Here, we report a single catalyst that cross-couples styrenes benzyl bromides iterative outer-sphere metal–ligand-carbon interactions. Each partner forms stabilized radical intermediate, yet heterocoupled products predominate. The system is redox-neutral and, thus, avoids exogenous oxidants, resulting in simple scalable conditions. Numerous variations of alkene hydrobenzylation are made possible, including access to the privileged heterodibenzyl (1,2-diarylethane) motif challenging quaternary carbon variants.

Language: Английский

Citations

19

Electrophotocatalytic Reductive 1,2‐Diarylationof Alkenes with Aryl Halides and Cyanoaromatics DOI

Liang Zeng,

Jing‐Hao Qin,

Gui‐Fen Lv

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(16), P. 1921 - 1930

Published: April 7, 2023

Comprehensive Summary The radical‐mediated reductive functionalization of aryl halides has been extensively studied. However, the related intermolecular 1,2‐diarylation alkenes, using as radical sources, remains unexplored. Herein, a new electrophotocatalytic alkenes is reported and cyanoaromatics to produce polyarylated alkanes. Using synergistic cathodic reduction visible‐light photoredox catalysis, various electron‐rich electron‐deficient are combined with characterize broad substrate scope, excellent functional group compatibility, selectivity this reaction. Mechanistic investigations reveal that reaction may proceed via process initiated by generation radicals from terminated radical‐radical coupling cyanoaromatic anions.

Language: Английский

Citations

36

Electroreductive Remote Benzylic C(sp3)–H Arylation of Aliphatic Ethers Using Cyanoarenes for the Synthesis of α-(Hetero)aryl Ethers DOI

Liang Zeng,

Hua-Zhan Ren,

Gui‐Fen Lv

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(12), P. 2440 - 2444

Published: March 19, 2024

An iodoarene-driven electroreductive remote C(sp3)–H arylation of unsymmetrical 1-(o-iodoaryl)alkyl ethers with cyanoarenes for the site selective synthesis α-(hetero)aryl is developed. With introduction as both aryl sources and electron transfer mediators, this method includes an strategy to enable regiocontrollable formation two new bonds, one C(sp2)–H bond, C(sp2)–C(sp3) in a single reaction step through sequence halogen atom (XAT), hydrogen (HAT), radical–radical coupling, decyanation.

Language: Английский

Citations

12

Electroreductive Arylcarboxylation of Styrenes with CO2 and Aryl Halides via a Radical–Polar Crossover Mechanism DOI

Fenfen Xie,

Fen Han,

Qian Su

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(21), P. 4427 - 4432

Published: May 17, 2024

2,3-Diaryl propanoic acids are important structures as a result of their widespread presence in numerous bioactive compounds. However, the limitations existing synthetic techniques include requirement for costly catalysts and limited substrates. Here, we developed novel electroreductive arylcarboxylation alkenes with CO2 based on radical–polar crossover pathway assisted by easily accessible dimethyl terephthalate reductive mediator. This method will provide an efficient strategy synthesis 2,3-diarylpropanoic acids.

Language: Английский

Citations

10

Ni-Catalyzed Regioselective Alkylarylation of Unactivated Alkenes in Amines Enabled by Cooperative Ligand Effects of Nitriles and Electron-Deficient Alkenes DOI

Vivek Aryal,

Supuni I. N. Hewa Inaththappulige,

Ayush Acharya

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(2), P. 1667 - 1676

Published: Jan. 7, 2025

We report a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ- and δ,ε-alkenylamines with aryl halides alkylzinc reagents. The reaction is enabled by amine coordination can use all primary, secondary, tertiary amines. constructs two new C(sp3)-C(sp3) C(sp3)-C(sp2) bonds produces δ- ε-arylamines C(sp3)-branching at the γ- δ-positions. A variety heteroaryl iodides both primary secondary reagents be used as coupling carbon sources. Mechanistic studies suggest that cooperative effect organic nitriles electron-deficient (EDAs) ligands.

Language: Английский

Citations

1

Electroreductive hydroxy fluorosulfonylation of alkenes DOI Creative Commons
Qingyuan Feng, Tianyu He, Shencheng Qian

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Dec. 13, 2023

An electroreductive strategy for radical hydroxyl fluorosulfonylation of alkenes with sulfuryl chlorofluoride and molecular oxygen from air is described. This mild protocol displays excellent functional group compatibility, broad scope, good scalability, providing convenient access to diverse β-hydroxy sulfonyl fluorides. These fluoride products can be further converted valuable aliphatic fluorides, β-keto β-alkenyl Further, some these showed inhibitory activity against Botrytis cinerea or Bursaphelenchus xylophilus, which could useful potent agrochemical discovery. Preliminary mechanistic studies indicate that this transformation achieved through rapid O2 interception by the alkyl subsequent reduction peroxy radical, outcompete other side reactions such as chlorine atom transfer, hydrogen Russell fragmentation.

Language: Английский

Citations

18

Electroreduction strategy: a sustainable tool for the generation of aryl radicals DOI
Xiaoqing Xie,

Wei Zhou,

Ruchun Yang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(15), P. 4318 - 4342

Published: Jan. 1, 2024

This review primarily focuses on the generation of aryl radicals via an electroreduction strategy, and systematically elaborates synthetic applications, scope, limitations substrates.

Language: Английский

Citations

9

Electroreductive deuteroarylation of alkenes enabled by an organo-mediator DOI Creative Commons
Xinling Li, Jianfeng Zhou,

Weijie Deng

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(29), P. 11418 - 11427

Published: Jan. 1, 2024

An environmentally friendly electroreduction approach is disclosed for site-specific introduction of deuterium via anti-Markovnikov selective deuteroarylation alkenes and aryl iodides with bipyridine as a mediator D 2 O ‘D’ source.

Language: Английский

Citations

8