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

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(16), С. 1913 - 1928

Опубликована: Апрель 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.

Язык: Английский

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

Chemical Society Reviews, Год журнала: 2023, Номер 53(1), С. 263 - 316

Опубликована: Дек. 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)

Язык: Английский

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Direct Deprotonative Functionalization of α,α‐Difluoromethyl Ketones using a Catalytic Organosuperbase

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(10)

Опубликована: Янв. 5, 2023

The deprotonative functionalization of α,α-difluoromethyl ketones is described herein. Using a catalytic organosuperbase and silane additive, the corresponding difluoroenolate could be generated trapped with aldehydes to deliver various α,α-difluoro-β-hydroxy in high yields. This new strategy tolerates numerous functional groups represents access by direct deprotonation difluoromethyl unit. diastereoselective version reaction was also investigated d.r. up 93 : 7. Several transformations were performed demonstrate synthetic potential these ketones. In addition, this method has been extended use other electrophiles such as imines chalcogen derivatives, sulfoxide nucleophile, thus leading diversity difluoromethylene compounds.

Язык: Английский

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Light-induced aryldifluoromethyl-sulfonylation/thioetherification of alkenes using arenethiolates as a photoreductant and sulfur source

Green Chemistry, Год журнала: 2023, Номер 25(22), С. 9292 - 9300

Опубликована: Янв. 1, 2023

A novel ATRA reaction was developed from simple and widely accessible alkenes, thiols, trifluoromethylarenes vis photo-induced EDA complex strategy. Several complicated bioactive molecules undergo smoothly the one-pot photosynthetic process.

Язык: 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, Год журнала: 2024, Номер 11(5), С. 1305 - 1313

Опубликована: Янв. 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.

Язык: Английский

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Controlled monodefluorination and alkylation of C(sp³)–F bonds by lanthanide photocatalysts: importance of metal–ligand cooperativity

Chemical Science, Год журнала: 2022, Номер 13(47), С. 14090 - 14100

Опубликована: Янв. 1, 2022

The controlled functionalization of a single fluorine in CF

Язык: Английский

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Cascade C–H Activation and Defluorinative Annulation of 2-Arylbenzimidazoles with α-Trifluoromethyl-α-diazoketones: Modular Assembly of 6-Fluorobenzimidazo[2,1-a]isoquinolines

Organic Letters, Год журнала: 2023, Номер 25(26), С. 4770 - 4775

Опубликована: Июнь 26, 2023

A novel Ru-catalyzed redox-neutral [4+2] cyclization of 2-arylbenzimidazoles with α-trifluoromethyl-α-diazoketones has been achieved through sequential C-H activation and defluorinative annulation. This synthetic protocol unlocks modular expeditious access to 6-fluorobenzimidazo[2,1-a]isoquinolines high efficiency excellent functional group compatibility. The resultant monofluorinated heterocyclic products can readily diversified by various nucleophiles.

Язык: Английский

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Rh‐Catalyzed Hydration/C−F Bond Cleavage of Fluorinated Diazoalkanes Enabling Synthesis of α‐Fluoro‐β‐ketophosphonates

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(17), С. 2883 - 2887

Опубликована: Июль 21, 2023

Abstract (β‐Diazo‐α,α‐difluoroethyl)phosphonates have been emerging as useful building blocks in organic synthetic chemistry recent years, which can be used diazo analog or masked carbene for the rapid assembly of difluoromethylene phosphonate‐containing compounds. Herein, we elaborate a method synthesis α‐fluoro‐β‐ketophosphonates from hydration/C−F bond cleavage situ generated (β‐amino‐α,α‐difluoroethyl)phosphonates via Rh‐carbene intermediate. Divers are tolerated this reaction affording good yields. This water coupling partner, represents (β‐diazo‐α,α‐difluoroethyl)phosphonates and also generating bioactive α‐fluoro‐β‐ketophosphonates.

Язык: Английский

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Selective Defluoroalkylation and Hydrodefluorination of Trifluoromethyl Groups Photocatalyzed by Dihydroacridine Derivatives

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(24), С. 17284 - 17296

Опубликована: Дек. 6, 2023

The selective functionalization of trifluoromethyl groups through C-F cleavage poses a significant challenge due to the high bond energy C(sp3)-F bonds. Herein, we present dihydroacridine derivatives as photocatalysts that can functionalize with various alkenes under mild conditions. Mechanistic studies and DFT calculations revealed upon irradiation, exhibit reducibility function for reductive defluorination. This process involves sequential single-electron transfer mechanism. research provides valuable insights into properties photocatalysts, highlighting importance maintaining planar conformation large conjugated system optimal catalytic activity. These findings facilitate efficient reduction inert chemical

Язык: Английский

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Recent Advance in the C−F Bond Functionalization of Trifluoromethyl Aromatic and Carbonyl Compounds

ChemCatChem, Год журнала: 2023, Номер 16(8)

Опубликована: Дек. 28, 2023

Abstract The selective C−F bonds functionalization in available trifluoromethyl compounds is an economic route for obtaining high‐value organic fluorine compounds. However, due to the high dissociation energy group, strength of bond decreases continuously during defluorination, posing a challenge modifying such molecules without over‐conversion. Over past few years, there has been significant progress developing efficient methods constructing difluoromethylene unit, using approaches as radical chemistry, photochemistry, electrochemistry, and organometallic chemistry. These involve difluorocarbon radicals, cations, anions, carbenes intermediates. In this review, we summarized recent five years research achievements field single cleavage aromatic carbonyl gain diverse difluoromethylene‐containing via different intermediate strategies.

Язык: Английский

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