Paired electrolysis-enabled nickel-catalyzed enantioselective reductive cross-coupling between α-chloroesters and aryl bromides DOI Creative Commons
Dong Liu,

Zhao‐Ran Liu,

Zhenhua Wang

и другие.

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Ноя. 28, 2022

Electrochemical asymmetric catalysis has emerged as a sustainable and promising approach to the production of chiral compounds utilization both anode cathode working electrodes would provide unique for organic synthesis. However, precise matching rate electric potential anodic oxidation cathodic reduction make such idealized electrolysis difficult achieve. Herein, cross-coupling between α-chloroesters aryl bromides is probed model reaction, wherein alkyl radicals are generated from through sequential oxidative electron transfer process at anode, while nickel catalyst reduced lower state cathode. Radical clock studies, cyclic voltammetry analysis, paramagnetic resonance experiments support synergistic involvement redox events. This electrolytic method provides an alternative avenue that could find significant utility in

Язык: Английский

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications DOI Creative Commons
Xiaopeng Peng, Abdur Rahim, Weijie Peng

и другие.

Chemical Reviews, Год журнала: 2023, Номер 123(4), С. 1364 - 1416

Опубликована: Янв. 17, 2023

Hypervalent aryliodoumiums are intensively investigated as arylating agents. They excellent surrogates to aryl halides, and moreover they exhibit better reactivity, which allows the corresponding arylation reactions be performed under mild conditions. In past decades, acyclic aryliodoniums widely explored However, unmet need for is improvement of their notoriously low reaction economy because coproduced iodides during often wasted. Cyclic have intrinsic advantage in terms economy, started receive considerable attention due valuable synthetic applications initiate cascade reactions, can enable construction complex structures, including polycycles with potential pharmaceutical functional properties. Here, we summarizing recent advances made research field cyclic aryliodoniums, nascent design aryliodonium species applications. First, general preparation typical diphenyl iodoniums described, followed by heterocyclic monoaryl iodoniums. Then, initiated arylations coupled subsequent domino summarized construct polycycles. Meanwhile, building biaryls axial atropisomers discussed a systematic manner. Finally, very advance employed halogen-bonding organocatalysts described.

Язык: Английский

Процитировано

69
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

и другие.

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Апрель 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.

Язык: Английский

Процитировано

57
Designing efficient catalysts for electrocatalytic organic synthesis: From electronic structure to adsorption behavior DOI Creative Commons
Chunming Yang, Le Zhang, Yuxuan Lu

и другие.

Matter, Год журнала: 2024, Номер 7(2), С. 456 - 474

Опубликована: Янв. 21, 2024

Язык: Английский

Процитировано

26
Recent Advances and Perspectives on Coupled Water Electrolysis for Energy‐Saving Hydrogen Production DOI Creative Commons
Jiachen Li,

Yuqiang Ma,

Xiaogang Mu

и другие.

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 7, 2025

Abstract Overall water splitting (OWS) to produce hydrogen has attracted large attention in recent years due its ecological‐friendliness and sustainability. However, the efficiency of OWS been forced by sluggish kinetics four‐electron oxygen evolution reaction (OER). The replacement OER alternative electrooxidation small molecules with more thermodynamically favorable potentials may fundamentally break limitation achieve production low energy consumption, which also be accompanied value‐added chemicals than or electrochemical degradation pollutants. This review critically assesses latest discoveries coupled various OWS, including alcohols, aldehydes, amides, urea, hydrazine, etc. Emphasis is placed on corresponding electrocatalyst design related mechanisms (e.g., dual hydrogenation N–N bond breaking hydrazine C═N regulation urea inhibit hazardous NCO − NO productions, etc.), along emerging reactions (electrooxidation tetrazoles, furazans, iodide, quinolines, ascorbic acid, sterol, trimethylamine, etc.). Some new decoupled electrolysis self‐powered systems are discussed detail. Finally, potential challenges prospects highlighted aid future research directions.

Язык: Английский

Процитировано

2
Nanoarchitectonics for Coordination Asymmetry and Related Chemistry DOI Open Access
Katsuhiko Ariga, Mitsuhiko Shionoya

Bulletin of the Chemical Society of Japan, Год журнала: 2020, Номер 94(3), С. 839 - 859

Опубликована: Дек. 14, 2020

Abstract Nanoarchitectonics is a concept envisioned to produce functional materials from nanoscale units through fusion of nanotechnology with other scientific disciplines. For component selection, coordination complexes metallic elements have wider variety element selection because cover ca. 80% the periodic table elements. Application nanoarchitectonics approaches chemistry leads huge expansion this much range Especially, asymmetry strategy architects asymmetrical and/or chiral structures electronic states formation metal complexes, leading material systems in certain anisotropy and selectivity. This review article presents collecting recent examples field asymmetry. Introduced are classified into several categories various viewpoints: (i) basic molecular designs; (ii) specific features depending on interfacial media, space contact bio-functions; (iii) functions; (iv) supporting techniques such as analyses theory.

Язык: Английский

Процитировано

95
Tunable Electrochemical C−N versus N−N Bond Formation of Nitrogen‐Centered Radicals Enabled by Dehydrogenative Dearomatization: Biological Applications DOI

Shide Lv,

Xiao-Xin Han,

Jianyong Wang

и другие.

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(28), С. 11583 - 11590

Опубликована: Март 23, 2020

Abstract Herein, an environmentally friendly electrochemical approach is reported that takes advantage of the captodative effect and delocalization to generate nitrogen‐centered radicals (NCRs). By changing reaction parameters electrode material feedstock solubility, dearomatization enabled a selective dehydrogenative C−N versus N−N bond formation reaction. Hence, pyrido[1,2‐ ]benzimidazole tetraarylhydrazine frameworks were prepared through sustainable transition‐metal‐ exogenous oxidant‐free strategy with broad generality. Bioactivity assays demonstrated ]benzimidazoles displayed antimicrobial activity cytotoxicity against human cancer cells. Compound 21 exhibited good photochemical properties large Stokes shift (approximately 130 nm) was successfully applied subcellular imaging. A preliminary mechanism investigation density functional theory (DFT) calculations revealed possible pathway.

Язык: Английский

Процитировано

92
Versatile Tools for Understanding Electrosynthetic Mechanisms DOI
Eric C.R. McKenzie, Seyyedamirhossein Hosseini, Ana G. Couto Petro

и другие.

Chemical Reviews, Год журнала: 2021, Номер 122(3), С. 3292 - 3335

Опубликована: Дек. 17, 2021

Electrosynthesis is a popular, green alternative to traditional organic methods. Understanding the mechanisms not trivial yet necessary optimize reaction processes. To this end, multitude of analytical tools available identify and quantitate products intermediates. The first portion review serves as guide that underscores electrosynthesis fundamentals, including instrumentation, electrode selection, impacts electrolyte solvent, cell configuration, methods electrosynthesis. Next, broad base techniques aid in mechanism elucidation are covered detail. These divided into electrochemical, spectroscopic, chromatographic, microscopic, computational. Technique selection dependent on predicted pathways electrogenerated Often, combination must be utilized ensure accuracy proposed model. conclude, future prospects aim enhance field discussed.

Язык: Английский

Процитировано

92
Progress in Electrochemical Trifluoromethylation Reactions DOI
Rasmi P. Bhaskaran, Beneesh P. Babu

Advanced Synthesis & Catalysis, Год журнала: 2020, Номер 362(23), С. 5219 - 5237

Опубликована: Окт. 13, 2020

Abstract The importance of fluorinated organic molecules in drugs and pharmaceuticals led to the development several synthetic methods for introducing fluorine into bioactive trifluoromethylation is one key approaches same. Electrochemical synthesis has emerged as most sustainable, green strategies recent years new developments electroorganic also focus on electrochemical compounds. A considerable number reports have appeared literature this review surveys all reactions. This highly sustainable trifluoromethylating protocol will emerge further soon pave way more energy‐efficient protocols. magnified image

Язык: Английский

Процитировано

87
Alkene versus alkyne reactivity in unactivated 1,6-enynes: regio- and chemoselective radical cyclization with chalcogens under metal- and oxidant-free conditions DOI
Mohana Reddy Mutra, Vishal Suresh Kudale, Jing Li

и другие.

Green Chemistry, Год журнала: 2020, Номер 22(7), С. 2288 - 2300

Опубликована: Янв. 1, 2020

Substituted pyrrolidine derivatives are obtained via regio- and chemoselective 5-exo-dig radical cyclization of unactivated 1,6-enynes with chalcogens under metal- oxidant-free conditions.

Язык: Английский

Процитировано

82
Electrochemical Desaturative β‐Acylation of Cyclic N‐Aryl Amines DOI
Tian Feng, Siyi Wang, Yin Liu

и другие.

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(6)

Опубликована: Дек. 8, 2021

Abstract Herein, we disclose a straightforward, robust, and simple route to access β‐substituted desaturated cyclic amines via an electrochemically driven desaturative β‐functionalization of amines. This transformation is based on multiple single‐electron oxidation processes using catalytic amounts ferrocene. The reaction proceeds in the absence stoichiometric electrolyte under mild conditions, affording desired products with high chemo‐ regioselectivity. was tolerant broad range substrates also enables late‐stage β‐C(sp 3 )−H acylation potentially valuable products. Preliminary mechanistic studies voltammetry reveal key role ferrocene as redox mediator reaction.

Язык: Английский

Процитировано

80