Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

Advanced Synthesis & Catalysis, Год журнала: 2021, Номер 364(2), С. 234 - 267

Опубликована: Ноя. 29, 2021

Abstract Fluorine‐containing moieties are widely used in the pharmaceutical, agrochemical, and material fields. Thus, these structures of immense interest fields organic synthesis medicinal chemistry. Among various fluorinated groups, difluoromethyl unit has drawn increasing attention due to its unique pharmaceutical properties. In recent years, several methods for difluoromethylated compounds have been rapidly developed. However, most treat aromatic with excess difluoromethylating reagents, which often contain organometallic compounds, so transformations generally less environmentally friendly atom‐economical. this review, we summarize development new motifs or difluoroalkenes from trifluoromethylated trifluoromethyl alkenes via single C( sp 3 )−F bond cleavage. magnified image

Язык: Английский

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Photochemical and electrochemical strategies in C–F bond activation and functionalization

Organic Chemistry Frontiers, Год журнала: 2021, Номер 9(3), С. 853 - 873

Опубликована: Дек. 7, 2021

The recent advances in photochemical or electrochemical C–F bond activation and functionalization have been summarized discussed.

Язык: Английский

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Photocatalytic defluoroalkylation and hydrodefluorination of trifluoromethyls using o-phosphinophenolate

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

Опубликована: Янв. 17, 2022

Under visible light irradiation, o-phosphinophenolate functions as an easily accessible photoredox catalyst to activate trifluoromethyl groups in trifluoroacetamides, trifluoroacetates, and (hetero)arenes deliver corresponding difluoromethyl radicals. It works relay with a thiol hydrogen atom transfer (HAT) enable selective defluoroalkylation hydrodefluorination. The reaction allows for the facile synthesis of broad scope difluoromethylene-incorporated carbonyl (hetero)aromatic compounds, which are valuable fluorinated intermediates interest pharmaceutical industry. ortho-diphenylphosphino substituent, is believed facilitate photoinduced electron transfer, plays essential role redox reactivity phenolate. In addition groups, pentafluoroethyl could also be selectively defluoroalkylated.

Язык: Английский

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Arenethiolate as a Dual Function Catalyst for Photocatalytic Defluoroalkylation and Hydrodefluorination of Trifluoromethyls

ACS Catalysis, Год журнала: 2022, Номер 12(7), С. 4103 - 4109

Опубликована: Март 18, 2022

Thiol is known to act as a hydrogen atom transfer catalyst working in synergy with photocatalyst photoredox catalysis, but we report herein that an arene thiolate appropriate substituent can be photoactivated under visible light function both strongly reducing electron-donating redox and HAT enable catalytic C–F activation of trifluoromethyl substrates for selective hydrodefluorination coupling various alkenes the presence formate salts. These reactions demonstrate promising utility arenethiolates dual photocatalysts. The synthetic this method demonstrated by broad scope amenable substrates, including trifluoromethylated (hetero)arenes, trifluoroacetates, trifluoroacetamides, which exhibited high levels chemoselectivity. reaction efficacy allows site-selective late-stage functionalization multitrifluoromethylated bioactive compounds pharmaceuticals

Язык: Английский

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Perfluorocyclobutyl-containing transparent polyimides with low dielectric constant and low dielectric loss

Polymer Chemistry, Год журнала: 2022, Номер 13(26), С. 3949 - 3955

Опубликована: Янв. 1, 2022

The combination of loose chain packing and high fluoro content endows PFCB-containing polyimides with excellent optical transparency dielectric properties.

Язык: Английский

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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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A review of frustrated Lewis pair enabled monoselective C–F bond activation

Chemical Science, Год журнала: 2024, Номер 15(8), С. 2712 - 2724

Опубликована: Янв. 1, 2024

Frustrated Lewis pair (FLP) bond activation chemistry has greatly developed over the last two decades since seminal report of metal-free reversible hydrogen activation. Recently, FLP systems have been utilized to allow monoselective C-F (at equivalent sites) in polyfluoroalkanes. The problem 'over-defluorination' functionalization polyfluoroalkanes (where multiple fluoro-positions are uncontrollably functionalized) a long-standing chemical fluorocarbon for 80 years. mediated is complementary other solutions address and offers several advantages unique opportunities. This perspective highlights some these opportunities places development into context wider effort overcome 'over-defluorination'.

Язык: Английский

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Recent Advances in C-F Bond Cleavage Enabled by Visible Light Photoredox Catalysis

Molecules, Год журнала: 2021, Номер 26(22), С. 7051 - 7051

Опубликована: Ноя. 22, 2021

The creation of new bonds via C-F bond cleavage readily available per- or oligofluorinated compounds has received growing interest. Using such a strategy, myriad valuable partially fluorinated products can be prepared, which otherwise are difficult to make by the conventional formation methods. Visible light photoredox catalysis been proven as an important and powerful tool for defluorinative reactions due its mild, easy handle, environmentally benign characteristics. Compared classical activation that proceeds two-electron processes, radicals key intermediates using visible catalysis, providing modes bonds. In this review, summary light-promoted since 2018 was presented. contents were classified fluorosubstrates, including polyfluorinated arenes, gem-difluoroalkenes, trifluoromethyl alkenes. An emphasis is placed on discussion mechanisms limitations these reactions. Finally, my personal perspective future development rapidly emerging field provided.

Язык: Английский

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A Base-Promoted Reductive Coupling Platform for the Divergent Defluorofunctionalization of Trifluoromethylarenes

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(29), С. 13032 - 13038

Опубликована: Июль 14, 2022

We report a trifluoromethylarene reductive coupling method that dramatically expands the scope of difluorobenzylic substructures accessible

Язык: Английский

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