Contemporary synthetic strategies in organofluorine chemistry

Nature Reviews Methods Primers, Год журнала: 2021, Номер 1(1)

Опубликована: Июль 8, 2021

Язык: Английский

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Trifluoromethyl Thianthrenium Triflate: A Readily Available Trifluoromethylating Reagent with Formal CF₃⁺, CF₃^•, and CF₃^– Reactivity

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(20), С. 7623 - 7628

Опубликована: Май 14, 2021

Here we report the synthesis and application of trifluoromethyl thianthrenium triflate (TT-CF3+OTf–) as a novel trifluoromethylating reagent, which is conveniently accessible in single step from thianthrene triflic anhydride. We demonstrate use TT-CF3+OTf– electrophilic, radical, nucleophilic trifluoromethylation reactions.

Язык: Английский

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Fluorinated Perylene‐Diimides: Cathode Interlayers Facilitating Carrier Collection for High‐Performance Organic Solar Cells

Advanced Materials, Год журнала: 2022, Номер 34(32)

Опубликована: Июнь 21, 2022

Abstract Organic solar cells (OSCs) have experienced rapid progress with the innovation of near‐infrared (NIR)‐absorbing small‐molecular acceptors (SMAs), while unique electronic properties SMAs raise new challenges in relation to cathode engineering for effective electron collection. To address this issue, two fluorinated perylene‐diimides (PDIs), PDINN‐F and PDINN‐2F, are synthesized by a simple fluorination method, application as interlayer (CIL) materials. The bay‐fluorinated PDI‐based CILs possess lower lowest unoccupied molecular orbital (LUMO) energy level ≈−4.0 eV, which improves alignment at NIR‐SMAs (such BTP‐eC9)/CIL favorable extraction efficiency. monofluorinated shows higher mobility better improved interfacial compatibility. PDINN‐F‐based OSCs PM6:BTP‐eC9 active layer exhibit an enhanced fill factor larger short‐circuit current density, leading high power conversion efficiency (PCE) exceeding 18%. devices CIL retain more than 80% their initial PCE after operating maximum point under continuous illumination 750 h. This work prescribes facile, cost‐effective, scalable method preparation stable, high‐performance CILs, instilling promise NIR‐SMAs‐based moving forward.

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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Strategies for Nucleophilic C(sp³)–(Radio)Fluorination

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(18), С. 9928 - 9950

Опубликована: Апрель 24, 2023

This Perspective surveys the progress and current limitations of nucleophilic fluorination methodologies. Despite long rich history C(sp3)–F bond construction in chemical research, inherent challenges associated with this transformation have largely constrained to a privileged reaction platform. In recent years, Doyle group─along many others─has pursued study development intent generating deeper mechanistic understanding, developing user-friendly reagents, contributing invention synthetic methods capable enabling radiofluorination. Studies from our laboratory are discussed along developments others field. Fluoride reagent implications identity highlighted. We also outline space inaccessible by technologies series future directions field that can potentially fill existing dark spaces.

Язык: Английский

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Fluorine-a small magic bullet atom in the drug development: perspective to FDA approved and COVID-19 recommended drugs

Chemical Papers, Год журнала: 2023, Номер 77(8), С. 4085 - 4106

Опубликована: Апрель 13, 2023

Язык: Английский

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Engineering non-haem iron enzymes for enantioselective C(sp3)–F bond formation via radical fluorine transfer

Nature Synthesis, Год журнала: 2024, Номер 3(8), С. 958 - 966

Опубликована: Март 28, 2024

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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Fluorination and Fluoroalkylation Reactions Mediated by Hypervalent Iodine Reagents

Advanced Synthesis & Catalysis, Год журнала: 2020, Номер 362(20), С. 4256 - 4292

Опубликована: Авг. 4, 2020

Abstract This review summarizes the progress in fluorination and fluoroalkylation of electron‐rich systems with diverse fluorine (F) fluoroalkyl (R fn ) reagents employing hypervalent iodine compounds as initiators last few decades. Because strong electrophilicity, high oxidizing properties, low toxicity, air moisture stability, ready availability, ease handling, mild reaction conditions, have been widely utilized modern organic chemistry. In particular, use to initiate C−F C−R =CF 2 H, CF 3 , perfluoroalkyl, OCH SCF SeCF etc) bond formation has increasingly developed. these reactions, behave powerful oxidants or electrophiles activate fluorination/fluoroalkylation reagents, transition‐metal catalysts, substrates situ form electrophilic radical intermediates, which subsequently participate fluorination, difluoromethylation, trifluoromethylation, perfluoroalkylation, trifluoroethoxylation, fluoroalkylthiolation, trifluoromethylselenolation others under conditions. Although great achievements made this area, they are just initial phase still require a wide scope for improvement. It is anticipated that will draw much attention from chemistry community inspire more contributions development new hypervalent‐iodine‐mediated reactions. magnified image

Язык: Английский

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A general strategy for C(sp3)–H functionalization with nucleophiles using methyl radical as a hydrogen atom abstractor

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Ноя. 29, 2021

Abstract Photoredox catalysis has provided many approaches to C(sp 3 )–H functionalization that enable selective oxidation and )–C bond formation via the intermediacy of a carbon-centered radical. While highly enabling, radical is largely mediated by electrophilic reagents. Notably, nucleophilic reagents represent an abundant practical reagent class, motivating interest in developing general strategy with nucleophiles. Here we describe transforms bonds into carbocations sequential hydrogen atom transfer (HAT) oxidative radical-polar crossover. The resulting carbocation functionalized variety nucleophiles—including halides, water, alcohols, thiols, electron-rich arene, azide—to effect diverse formations. Mechanistic studies indicate HAT methyl radical—a previously unexplored agent differing polarity those used photoredox catalysis—enabling new site-selectivity for late-stage functionalization.

Язык: Английский

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