Regiodivergent C−H Acylation of Arenes by Switching from Ionic‐ to Radical‐Type Chemistry Using NHC Catalysis DOI

Jannik Reimler,

Xiaoye Yu,

Nico Spreckelmeyer

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(27)

Published: April 24, 2023

The Friedel-Crafts acylation reaction, which belongs to the class of electrophilic aromatic substitutions is a highly valuable and versatile reaction in synthesis. Regioselectivity predictable determined by electronic as well steric factors (hetero)arene substrate. Herein, radical approach for arenes heteroarenes presented. C-H achieved through mild cooperative photoredox/NHC catalysis with cross-coupling an arene cation NHC-bound ketyl key step. As compared classical acylation, regiodivergent outcome observed upon switching from ionic mode. In these divergent reactions, aroyl fluorides act reagents both process.

Language: Английский

Electrocatalysis as an enabling technology for organic synthesis DOI
Luiz F. T. Novaes, Jinjian Liu, Yifan Shen

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(14), P. 7941 - 8002

Published: Jan. 1, 2021

Electrochemistry has recently gained increased attention as a versatile strategy for achieving challenging transformations at the forefront of synthetic organic chemistry. Electrochemistry's unique ability to generate highly reactive radical and ion intermediates in controlled fashion under mild conditions inspired development number new electrochemical methodologies preparation valuable chemical motifs. Particularly, recent developments electrosynthesis have featured an use redox-active electrocatalysts further enhance control over selective formation downstream reactivity these intermediates. Furthermore, electrocatalytic mediators enable proceed manner that is mechanistically distinct from purely methods, allowing subversion kinetic thermodynamic obstacles encountered conventional synthesis. This review highlights key innovations within past decade area electrocatalysis, with emphasis on mechanisms catalyst design principles underpinning advancements. A host oxidative reductive are discussed grouped according classification transformation nature electrocatalyst.

Language: Английский

Citations

872
Powering the Future: How Can Electrochemistry Make a Difference in Organic Synthesis? DOI Creative Commons
Tjark H. Meyer, Isaac Choi, Cong Tian

et al.

Chem, Journal Year: 2020, Volume and Issue: 6(10), P. 2484 - 2496

Published: Sept. 24, 2020

Language: Английский

Citations

377
Recent advances in organic electrosynthesis employing transition metal complexes as electrocatalysts DOI
Cong Ma, Ping Fang,

Zhao‐Ran Liu

et al.

Science Bulletin, Journal Year: 2021, Volume and Issue: 66(23), P. 2412 - 2429

Published: July 13, 2021

Language: Английский

Citations

293
Electrochemically Enabled, Nickel-Catalyzed Dehydroxylative Cross-Coupling of Alcohols with Aryl Halides DOI
Zijian Li, Wenxuan Sun,

Xianxu Wang

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(9), P. 3536 - 3543

Published: Feb. 23, 2021

As alcohols are ubiquitous throughout chemical science, this functional group represents a highly attractive starting material for forging new C–C bonds. Here, we demonstrate that the combination of anodic preparation alkoxy triphenylphosphonium ion and nickel-catalyzed cathodic reductive cross-coupling provides an efficient method to construct C(sp2)–C(sp3) bonds, in which free aryl bromides—both readily available chemicals—can be directly used as coupling partners. This paired electrolysis reaction features broad substrate scope bearing wide gamut functionalities, was illustrated by late-stage arylation several structurally complex natural products pharmaceuticals.

Language: Английский

Citations

202
Green Chemistry: Electrochemical Organic Transformations via Paired Electrolysis DOI
Najoua Sbei, Tomas Hardwick, Nisar Ahmed

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2021, Volume and Issue: 9(18), P. 6148 - 6169

Published: April 27, 2021

Paired electrolysis is highly valuable from the viewpoint of efficiency as well atom and energy economies. In order to optimize latter two for chemical reactions, development paired electrochemical processes necessary. When both electrodes in an cell (divided undivided) are applied working electrodes, sides (oxidation reduction) yield compounds, this ideal phenomena defined electrosynthesis. This offers opportunity reduce spent time, when compared with a single system that only used achieve product interest, while ignoring other side (anodic or cathodic). case, 200% current could be achieved during electrosynthesis using cathodic anodic provide same product. efficient green process and, therefore, beneficial preserving resources minimizing waste. However, beneficial, oxidation reduction must compatible counter losses equally ease separation purification electrode products. Greater efforts required perform more systematic rational approach optimal products under conditions. Nevertheless, new computational tools assistance matter. There considerable level adventure designing electrosynthetic accompanying opportunities design innovative powerful synthetic strategies. Herein, overview several examples electrosyntheses their advantages summarized will aid researchers develop greater understanding subject subsequently employ sustainable synthesis organic molecules.

Language: Английский

Citations

123
Aroyl Fluorides as Bifunctional Reagents for Dearomatizing Fluoroaroylation of Benzofurans DOI Creative Commons
Xiaoye Yu, Qingyuan Meng, Constantin G. Daniliuc

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(16), P. 7072 - 7079

Published: March 22, 2022

The 2,3-dihydrobenzofuran scaffold is widely found in natural products and biologically active compounds. Herein, dearomatizing 2,3-fluoroaroylation of benzofurans with aroyl fluorides as bifunctional reagents to access 2,3-difunctionalized dihydrobenzofurans reported. reaction that occurs by cooperative NHC/photoredox catalysis provides 3-aroyl-2-fluoro-2,3-dihydrobenzofurans moderate good yield high diastereoselectivity. Cascades proceed via radical/radical cross-coupling a benzofuran radical cation generated the photoredox cycle neutral ketyl formed through NHC cycle. redox-neutral transformation exhibits broad substrate scope functional group compatibility. With anhydrides reagents, aroyloxyacylation achieved strategy can also be applied

Language: Английский

Citations

122
Traditional and sustainable approaches for the construction of C–C bonds by harnessing C–H arylation DOI Creative Commons
Jagrit Grover, Gaurav Prakash, Nupur Goswami

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Feb. 28, 2022

Abstract Biaryl scaffolds are found in natural products and drug molecules exhibit a wide range of biological activities. In past decade, the transition metal-catalyzed C–H arylation reaction came out as an effective tool for construction biaryl motifs. However, traditional reactions have limitations like harsh conditions, narrow substrate scope, use additives etc. therefore encouraged synthetic chemists to look alternate greener approaches. This review aims draw general overview on bond formation C–C bonds with aid different methodologies, majorly highlighting sustainable

Language: Английский

Citations

82
Electrochemical oxidative C(sp3)–H cross-coupling with hydrogen evolution DOI

Zhaoliang Yang,

Wenyan Shi, Hesham Alhumade

et al.

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(3), P. 217 - 230

Published: Feb. 16, 2023

Language: Английский

Citations

68
Nickel/biimidazole-catalyzed electrochemical enantioselective reductive cross-coupling of aryl aziridines with aryl iodides DOI Creative Commons

Yun-Zhao Wang,

Zhenhua Wang, Inbal Lorena Eshel

et al.

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

Published: April 22, 2023

Here, we report an asymmetric electrochemical organonickel-catalyzed reductive cross-coupling of aryl aziridines with iodides in undivided cell, affording β-phenethylamines good to excellent enantioselectivity broad functional group tolerance. The combination cyclic voltammetry analysis the catalyst reduction potential as well electrode study provides a convenient route for reaction optimization. Overall, high efficiency this method is credited electroreduction-mediated turnover nickel instead metal reductant-mediated turnover. Mechanistic studies suggest radical pathway involved ring opening aziridines. statistical serves compare different design requirements photochemically and electrochemically mediated reactions under type mechanistic manifold.

Language: Английский

Citations

57
Paired Oxidative and Reductive Catalysis: Breaking the Potential Barrier of Electrochemical C(sp3)−H Alkenylation** DOI

Long Zou,

Xiaofan Wang,

Siqi Xiang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(24)

Published: April 1, 2023

Due to the intrinsic inertness of alkanes, strong oxidative conditions are typically required enable their C(sp3 )-H functionalization. Herein, a paired electrocatalysis strategy was developed by integrating catalysis with reductive in one cell without interference, which earth-abundant iron and nickel employed as anodic cathodic catalysts, respectively. This approach lowers previously high oxidation potential for alkane activation, enabling electrochemical functionalization at ultra-low ≈0.25 V vs. Ag/AgCl under mild conditions. Structurally diverse alkenes, including challenging all-carbon tetrasubstituted olefins, can be accessed using readily available alkenyl electrophiles.

Language: Английский

Citations

46