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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Sulfonyl Fluoride Synthesis through Electrochemical Oxidative Coupling of Thiols and Potassium Fluoride

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(30), С. 11832 - 11836

Опубликована: Июль 13, 2019

Sulfonyl fluorides are valuable synthetic motifs for a variety of applications, among which sulfur(VI) fluoride exchange-based "click chemistry" is currently the most prominent. Consequently, development novel and efficient methods to access these functional groups great interest. Herein, we report mild environmentally benign electrochemical approach prepare sulfonyl using thiols or disulfides, as widely available starting materials, in combination with KF, an inexpensive, abundant safe source. No additional oxidants nor catalysts required and, due reaction conditions, displays broad substrate scope, including alkyl, benzyl, aryl heteroaryl disulfides.

Язык: Английский

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Nucleophilic (Radio)Fluorination of Redox-Active Esters via Radical-Polar Crossover Enabled by Photoredox Catalysis

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(20), С. 9493 - 9500

Опубликована: Май 7, 2020

We report a redox-neutral method for nucleophilic fluorination of N-hydroxyphthalimide esters using an Ir photocatalyst under visible light irradiation. The provides access to broad range aliphatic fluorides, including primary, secondary, and tertiary benzylic fluorides as well unactivated that are typically inaccessible by due competing elimination. In addition, we show the decarboxylative conditions readily adapted radiofluorination with [18F]KF. propose reactions proceed two electron transfers between catalyst redox-active ester substrate afford carbocation intermediate undergoes subsequent trapping fluoride. Examples O- C-centered nucleophiles deoxyfluorination via N-hydroxyphthalimidoyl oxalates also presented, suggesting this approach may offer general blueprint affecting SN1 substitutions mild conditions.

Язык: Английский

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Visible Light Assisted Radical‐Polar/Polar‐Radical Crossover Reactions in Organic Synthesis

Advanced Synthesis & Catalysis, Год журнала: 2021, Номер 363(13), С. 3146 - 3169

Опубликована: Апрель 10, 2021

Abstract Chemists are generally familiar with polar reactions and radical reactions, in comparison, underdeveloped. In the last few years, however, novel concept of amalgamation above two form radical‐polar crossover (RPCO) polar‐radical (PRCO) has emerged as a valuable powerful tool. This methodology tends to bridge gap between well overcomes limitations both traditional chemistry. By bringing together unorthodox chemistry radicals orthodox carbocations carbanions, green quotient such is significantly improved. The development shaping up this area years synthetically important transformations summarised review. magnified image

Язык: Английский

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Recent Developments and Trends in Asymmetric Organocatalysis

European Journal of Organic Chemistry, Год журнала: 2022, Номер 26(1)

Опубликована: Окт. 17, 2022

Asymmetric organocatalysis has experienced a long and spectacular way since the early reports over century ago by von Liebig, Knoevenagel Bredig, showing that small (chiral) organic molecules can catalyze (asymmetric) reactions. This was followed impressive first highly enantioselective in second half of last century, until hype initiated 2000 milestone publications MacMillan List, which finally culminated 2021 Nobel Prize Chemistry. short Perspective aims at providing brief introduction to field looking on historical development more classical methods concepts, discussing selected advanced recent examples opened new directions diversity within this still growing field.

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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Enantioselective Transformations in the Synthesis of Therapeutic Agents

Chemical Reviews, Год журнала: 2023, Номер 123(15), С. 9397 - 9446

Опубликована: Июль 7, 2023

The proportion of approved chiral drugs and drug candidates under medical studies has surged dramatically over the past two decades. As a consequence, efficient synthesis enantiopure pharmaceuticals or their synthetic intermediates poses profound challenge to medicinal process chemists. significant advancement in asymmetric catalysis provided an effective reliable solution this challenge. successful application transition metal catalysis, organocatalysis, biocatalysis pharmaceutical industries promoted discovery by precise preparation enantio-enriched therapeutic agents, facilitated industrial production active ingredient economic environmentally friendly fashion. present review summarizes most recent applications (2008–2022) industry ranging from scales pilot levels. It also showcases latest achievements trends agents with state art technologies catalysis.

Язык: Английский

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Hydrodifluoromethylation of Alkenes with Difluoroacetic Acid

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(26), С. 8829 - 8833

Опубликована: Апрель 25, 2019

Abstract A facile method for the regioselective hydrodifluoromethylation of alkenes is reported using difluoroacetic acid and phenyliodine(III) diacetate in tetrahydrofuran under visible‐light activation. This metal‐free approach stands out as it uses inexpensive reagents, does not require a photocatalyst, displays broad functional group tolerance. The procedure also operationally simple scalable, provides access one step to high‐value building blocks application medicinal chemistry.

Язык: Английский

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Arenesulfonyl Fluoride Synthesis via Copper-Catalyzed Fluorosulfonylation of Arenediazonium Salts

Organic Letters, Год журнала: 2020, Номер 22(6), С. 2281 - 2286

Опубликована: Март 2, 2020

We report herein a general and practical copper-catalyzed fluorosulfonylation reaction of wide range abundant arenediazonium salts to smoothly prepare various arenesulfonyl fluorides using the 1,4-diazabicyclo[2.2.2]octane-bis(sulfur dioxide) adduct as convenient sulfonyl source in combination with KHF2 an ideal fluorine without need for additional oxidants. Interestingly, electronic character arene ring starting has significant impact on mechanistic pathway.

Язык: Английский

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Urea Derivatives as Functional Molecules: Supramolecular Capsules, Supramolecular Polymers, Supramolecular Gels, Artificial Hosts, and Catalysts

Chemistry - A European Journal, Год журнала: 2020, Номер 27(18), С. 5601 - 5614

Опубликована: Ноя. 13, 2020

Abstract Urea, which has both hydrogen bond acceptor and donor moieties, is an ideal structure for a supramolecular synthon. Various supramolecules having ureido group(s) have been widely developed. This article summarizes recent developments of urea derivatives that exhibit various functions: i) capsules form discrete urea–urea intermolecular bonds, ii) polymers continuous iii) gels iv) artificial host molecules based on the molecular recognition ability group, v) catalytic reactions developed by utilizing group.

Язык: Английский

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