Synthetic Advantages of Defluorinative C−F Bond Functionalization

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(49)

Опубликована: Авг. 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.

Язык: Английский

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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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Application of the Spin-Center Shift in Organic Synthesis

JACS Au, Год журнала: 2022, Номер 2(5), С. 1032 - 1042

Опубликована: Апрель 11, 2022

Spin-center shift (SCS) is a radical process involving 1,2-radical translocation along with two-electron ionic movement, such as elimination of an adjacent leaving group. Such was initially observed in some important biochemical transformations, and the unique property has also attracted considerable interest synthetic chemistry. Experimental, kinetic, well computational studies have been performed, series useful transformations developed applied organic synthesis based on SCS processes last 20 years. This Perspective overview mechanism.

Язык: Английский

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Synthesis of Fluorinated Compounds by Nickel-Catalyzed Defluorinative Cross-Coupling Reactions

ACS Catalysis, Год журнала: 2023, Номер 13(18), С. 12238 - 12268

Опубликована: Сен. 1, 2023

Organofluorine compounds have attracted extensive attention in various industrial fields due to their unique chemical and physical properties. Despite increasing demand a wide range of scientific fields, the synthesis organofluorine still faces several problems, such as difficulties handling fluorinating reagents control chemoselectivity. Compared with formation C–F bonds, activation functionalization carbon–fluorine bonds is very important but challenging topic synthetic chemistry. Due properties nickel, Ni-catalyzed defluorinative cross-couplings been greatly developed past few decades powerful strategies for construction fluorinated organic compounds. This Review summarizes advances cross-coupling aryl fluorides, gem-difluorovinyl trifluoromethyl

Язык: Английский

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Transition metal-free photochemical C–F activation for the preparation of difluorinated-oxindole derivatives

Chemical Science, Год журнала: 2023, Номер 14(9), С. 2379 - 2385

Опубликована: Янв. 1, 2023

The development of strategies for single and selective C-F bond activation represents an important avenue to overcome limitations in the synthesis valuable fluorine-containing compounds. synthetic medicinal research communities would benefit from new routes that access such relevant molecules a simple manner. Herein we disclose straightforward mechanistically distinct pathway generate gem-difluoromethyl radicals their installation onto N-arylmethacrylamides preparation difluorinated oxindole derivatives. To achieve operational simplicity, use readily available benzenethiol as photocatalyst under open-to-air conditions was developed, demonstrating facile multigram targeted fluorinated molecules. Additionally, dispersion-corrected density functional theory (DFT) empirical investigations provide basis support proposed reaction pathway, indicating arene thiolate is efficient organophotocatalyst this transformation.

Язык: Английский

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Divergent defluorocarboxylation of α-CF3 alkenes with formate via photocatalyzed selective mono- or triple C-F bond cleavage

Science China Chemistry, Год журнала: 2023, Номер 67(1), С. 368 - 373

Опубликована: Авг. 16, 2023

Язык: Английский

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Halogen‐Atom Transfer Enabled Catalytic Enantioselective Coupling to Chiral Trifluoromethylated Alkynes via Dual Nickel and Photocatalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(28)

Опубликована: Апрель 15, 2024

With halogen-atom transfer as an effective tool, a novel catalytic enantioselective protocol to generate chiral trifluoromethylated alkynes has been established by cooperative photoredox and nickel catalysis system, providing straightforward modular route access this type of product in good yields enantioselectivities. The process is essential for the reaction strategy offers another promising way utilize alkyl halides with highly negative reduction potentials. It firstly expands nickel-catalyzed asymmetric reductive cross-couplings organohalides from traditional single-electron transfer.

Язык: Английский

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Picking Two out of Three: Defluorinative Annulation of Trifluoromethyl Alkenes for the Synthesis of Monofluorinated Carbo‐ and Heterocycles

The Chemical Record, Год журнала: 2024, Номер 24(3)

Опубликована: Янв. 22, 2024

Abstract The increasing demand of organofluorine compounds in medicine, agriculture, and materials sciences makes sophisticated methods for their synthesis ever more necessary. Nowadays, not only the C−F bond formation but also selective cleavage readily available poly‐ or perfluorine‐containing have become powerful tools effective compounds. defluorinative cross‐coupling trifluoromethyl alkenes with various nucleophiles radical precursors an S N 2’ manner is a convergent route to access gem ‐difluoroalkenes, which turn react via V‐type reaction. If V reactions occur intramolecularly, dual allows facile assembly monofluorinated cyclic skeletons structural complexity diversity. In this personal account, we summarized advances field on basis coupling cyclization partners, including binucleophiles, alkynes, diradical bearing nucleophilic site. Accordingly, annulation can be achieved by base‐mediated sequential 2′/S reactions, transition metal catalyzed mediated photoredox catalysis, combination photocatalytic context seminal works others field, concise summary contributions authors offered.

Язык: Английский

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Decatungstate-Catalyzed Hydrosilylation of α-Trifluoromethylalkenes for Construction of α-Trifluoromethyl-β-silanes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 18, 2025

The hydrosilylation of alkenes is a pivotal transformation for the synthesis organosilanes; however, fluorine-containing limited due to facile β-fluoride elimination. Herein, by employing direct hydrogen atom transfer (HAT) catalyst, tetrabutylammonium decatungstate (TBADT), and using disulfide as co-catalyst, we have successfully developed mild photocatalytic α-trifluoromethylalkenes α-trifluoromethyl-β-silanes. Our method features conditions, good regioselectivity, compatibility. elimination was fully inhibited. A radical mechanism proposed based on preliminary results.

Язык: Английский

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Electrosynthetic C–F bond cleavage

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(34), С. 6707 - 6720

Опубликована: Янв. 1, 2022

Fluorinated organic compounds are common among pharmaceuticals, agrochemicals and materials. The significant strength of the C-F bond results in chemical inertness that, depending on context, is beneficial, problematic or simply a formidable synthetic challenge. Electrosynthesis rapidly expanding methodology that can enable new reactivity selectivity for cleavage formation bonds. Here, comprehensive overview synthetically relevant electrochemically driven protocols activation functionalization presented, including photoelectrochemical strategies.

Язык: Английский

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