Synthetic Advantages of Defluorinative C−F Bond Functionalization

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Aug. 22, 2023

Abstract Much progress has been made in the development of methods to both create compounds that contain C−F bonds and functionalize bonds. As such, are becoming common versatile synthetic functional handles. This review summarizes advantages defluorinative functionalization reactions for small molecule synthesis. The coverage is organized by type carbon framework fluorine attached mono‐ polyfluorinated motifs. main challenges, opportunities advances discussed each class organofluorine. Most text focuses on case studies illustrate how defluorofunctionalization can improve routes targets or properties enable unique mechanisms reactions. broader goal showcase incorporating exploiting design routes, improvement specific advent new methods.

Language: Английский

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Photo- and electro-chemical strategies for the activations of strong chemical bonds

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(1), P. 263 - 316

Published: Dec. 7, 2023

The employment of light and/or electricity - alternatively to conventional thermal energy unlocks new reactivity paradigms as tools for chemical substrate activations. This leads the development synthetic reactions and a vast expansion spaces. review summarizes recent developments in photo- electrochemical activation strategies functionalization strong bonds particularly carbon-heteroatom (C-X)

Language: Английский

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Recent Advances in the Electrochemical Defluorinative Transformations of C—F Bonds

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(16), P. 1913 - 1928

Published: April 24, 2024

Comprehensive Summary Organic fluorine compounds are ubiquitous and pivotally important organic molecules, yet their activation transformation have long been a formidable challenge due to the high energy low reactivity of C—F bonds. electrosynthesis, an environmentally benign synthetic method in chemistry, enables myriad chemical transformations without need for external redox reagents. In recent years, electrochemistry has emerged as powerful tool achieving bonds fluorine‐containing compounds. This review aims succinctly recapitulate latest advancements electrochemical defluorinative delve into reaction design, mechanistic insights, developmental prospects these methods. Key Scientists 1959, Lund was first pioneer electroreduction CF 3 CH group. Electrochemistry lately provided new opportunities efficient conversion fluorides. 2020, Zhou coworkers discovered carboxylation α‐CF alkenes. Lambert colleagues reported electrophotocatalytic amination aryl Electrochemical hydrodefluorination trifluoromethylketones developed by Lennox 2021. same year, Wang Guo disclosed radical alkylation alkenes with Katritzky salts alkyl precursors. Subsequently, Wu Liao described transition‐metal‐free, site‐selective arylation polyfluoroarenes (het)arenes using paired electrophotocatalysis. 2023, numerous efforts were made achieve bond activation. Xia organoboron‐controlled chemoselective sequential (deutero)hydrodefluorination trifluoroacetamides.

Language: Английский

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Electrostatic Field in Contact‐Electro‐Catalysis Driven C−F Bond Cleavage of Perfluoroalkyl Substances

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: March 1, 2024

Abstract Perfluoroalkyl substances (PFASs) are persistent and toxic to human health. It is demanding for high‐efficient green technologies remove PFASs from water. In this study, a novel PFAS treatment technology was developed, utilizing polytetrafluoroethylene (PTFE) particles (1–5 μm) as the catalyst low frequency ultrasound (US, 40 kHz, 0.3 W/cm 2 ) activation. Remarkably, system can induce near‐complete defluorination different structured PFASs. The underlying mechanism relies on contact electrification between PTFE water, which induces cumulative electrons surface, creates high surface voltage (tens of volts). Such generate abundant reactive oxygen species (ROS, i.e., O ⋅ − , HO⋅, etc.) strong interfacial electrostatic field (IEF 10 9 ~10 V/m). Consequently, IEF significantly activates molecules reduces energy barrier nucleophilic reaction. Simultaneously, co‐existence (PTFE*( e )) HO⋅ enables synergetic reduction oxidation its intermediates, leading enhanced thorough defluorination. US/PTFE method shows compelling advantages consumption, zero chemical input, few harmful intermediates. offers new promising solution effectively treating PFAS‐contaminated drinking

Language: Английский

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Electronically Ambivalent Hydrodefluorination of Aryl‐CF₃ groups enabled by Electrochemical Deep‐Reduction on a Ni Cathode

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(12)

Published: Jan. 27, 2023

We report a general procedure for the direct mono- and di-hydrodefluorination of ArCF

Language: Английский

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The electrochemical coupling reactions of organic halides compound in a valuable and practical manner for C C and C–heteroatom formation: An overview

Arabian Journal of Chemistry, Journal Year: 2024, Volume and Issue: 17(8), P. 105822 - 105822

Published: May 24, 2024

Owing to the environmental and energy problems nowadays, one of enormous challenges is expanding clean, renewable reduce destructive ecological effects chemical industries. Compared with other traditional processes, electrochemical method has some benefits, such as being selective, causing minor waste, working under mild conditions no external oxidizing or reducing reagents, making this approach more economical eco-friendly. Electrochemistry represents a powerful tool within synthetic organic chemistry. The development part chemistry intends performance reactions employing electrons, including adding removing electrons. Using electric current reagent advantages, simplicity reactions, accessibility materials, replacing toxic applying an eco-friendly environment. During last decades, there been much effort decrease usage fossil fuels, electricity emerged common source. conversion into leads new paths, naturally safe environmentally friendly. Developing electrochemistry approaches for performing high-performance essential reaction green strategy because utilization instead stoichiometric oxidants reductants. Due its helpful friendly ability produce reactive intermediates, advanced considerably in oxidative hydrogen evolution coupling sacrificial anode electroreduction. New developments focus on developing electrolytic catalysts,photoelectrocatalysis, bioelectrosynthesis, optimizing electrode paired electrolysis, artificial intelligence-assisted electrosynthesis. Thus, daily significant number construction projects possibilities electrochemistry. Electrochemical methods constructing compounds have tolerated renewal past decades. Organic wealthy background synthesis. We hope review helps attract attention from researchers by using processes laboratory industrial centers, which pollution create In review, organohalides synthesizing various products summarized discussed since 2000.

Language: Английский

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Performance and degradation pathway of florfenicol antibiotic by nitrogen-doped biochar supported zero-valent iron and zero-valent copper: A combined experimental and DFT study

Journal of Hazardous Materials, Journal Year: 2023, Volume and Issue: 459, P. 132172 - 132172

Published: July 29, 2023

Language: Английский

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New Indole Derivative Heterogeneous System for the Synergistic Reduction and Oxidation of Various Per-/Polyfluoroalkyl Substances: Insights into the Degradation/Defluorination Mechanism

Environmental Science & Technology, Journal Year: 2023, Volume and Issue: 57(50), P. 21459 - 21469

Published: Dec. 6, 2023

The hydrated electron (eaq-) system is typically suitable for degrading perfluoroalkyl substances (PFASs). To enhance eaq- utilization, we synthesized a new indole compound (DIHA) that forms stable nanospheres (100-200 nm) in water via supramolecular assembly. Herein, the DIHA nanoemulsion exhibits high degradation efficiencies toward broad category of PFASs, regardless headgroup, chain length, and branching structure, under UV (254 irradiation. strong adsorption PFAS on surface ensures its effective degradation/defluorination. Quenching experiments further demonstrated reaction took place nanospheres. This specific heterogeneous unveiled novel defluorination mechanisms differ from previously reported systems. First, photogenerated electrons nonselectively attacked multiple C-F bonds -CF2- chain. plays dominant degrading/defluorinating role system. Second, abundant hydroxyl radicals (•OH) were also produced, leading to synergistic reduction (by electron) oxidation •OH) single facilitates faster deeper different structured PFASs through pathways. mechanism inspires design innovative organo-heterogeneous systems possessing functions, thereby making them potentially treating PFAS-contaminated water.

Language: Английский

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Electrochemical nickel-catalysed defluoroalkylation ofgem-difluoroalkenes with alkyl halides

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(20), P. 7952 - 7958

Published: Jan. 1, 2023

Herein, a direct and efficient electrochemical method for the synthesis of monofluoroalkene products was promoted using gem -difluoroalkenes unactivated alkyl halides as starting materials with nickel catalyst.

Language: Английский

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Radical-mediated [3 + 2 + 1] annulation of α-polyfluoromethyl alkenes with arylisocyanates enabled by C(sp³)–F activation

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(5), P. 1305 - 1313

Published: Jan. 1, 2024

A conceptually novel single electron transfer strategy for C(sp3)–F activation-enabled [3 + 2 1] annulation of α-polyfluoromethyl alkenes is developed.

Language: Английский

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