Room Temperature Defluorination of Poly(tetrafluoroethylene) by a Magnesium Reagent DOI Creative Commons
Daniel J. Sheldon, Joseph M. Parr, Mark R. Crimmin

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(19), P. 10486 - 10490

Published: May 8, 2023

Perfluoroalkyl substances (PFAS) are pervasive in the environment. The largest single use material within PFAS compound class is poly(tetrafluoroethylene) (PTFE), a robust and chemically resistant polymer. Despite their widespread serious concerns about role as pollutants, methods for repurposing rare. Here we show that nucleophilic magnesium reagent reacts with PTFE at room temperature, generating molecular fluoride which easily separated from surface-modified turn can be used to transfer fluorine atoms small array of compounds. This proof-of-concept study demonstrates atomic content harvested reused chemical synthesis.

Language: Английский

Contemporary synthetic strategies in organofluorine chemistry DOI
Robert Britton, Véronique Gouverneur, Jin‐Hong Lin

et al.

Nature Reviews Methods Primers, Journal Year: 2021, Volume and Issue: 1(1)

Published: July 8, 2021

Language: Английский

Citations

212
Sulfonyl Fluoride Synthesis through Electrochemical Oxidative Coupling of Thiols and Potassium Fluoride DOI Creative Commons
Gabriele Laudadio, Aloisio de Andrade Bartolomeu,

Lucas M. H. M. Verwijlen

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(30), P. 11832 - 11836

Published: July 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.

Language: Английский

Citations

180
Nucleophilic (Radio)Fluorination of Redox-Active Esters via Radical-Polar Crossover Enabled by Photoredox Catalysis DOI
Eric Webb,

John B. Park,

Erin L. Cole

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(20), P. 9493 - 9500

Published: May 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.

Language: Английский

Citations

145
Visible Light Assisted Radical‐Polar/Polar‐Radical Crossover Reactions in Organic Synthesis DOI
Shivani Sharma, Jitender Singh, Anuj Sharma

et al.

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 363(13), P. 3146 - 3169

Published: April 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

Language: Английский

Citations

124
Recent Developments and Trends in Asymmetric Organocatalysis DOI Creative Commons
Olga Garcı́a Mancheño, Mario Waser

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 26(1)

Published: Oct. 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.

Language: Английский

Citations

85
Strategies for Nucleophilic C(sp3)–(Radio)Fluorination DOI
Isabelle Nathalie-Marie Leibler, Shivaani Gandhi, Makeda A. Tekle‐Smith

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(18), P. 9928 - 9950

Published: April 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.

Language: Английский

Citations

51
Enantioselective Transformations in the Synthesis of Therapeutic Agents DOI
Yang He,

Hanxiao Yu,

I. Stolarzewicz

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(15), P. 9397 - 9446

Published: July 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.

Language: Английский

Citations

43
Enantioconvergent nucleophilic substitution via synergistic phase-transfer catalysis DOI Creative Commons
C. J. Dooley, Francesco Ibba, Bence B. Botlik

et al.

Nature Catalysis, Journal Year: 2025, Volume and Issue: 8(2), P. 107 - 115

Published: Feb. 13, 2025

Language: Английский

Citations

2
Hydrodifluoromethylation of Alkenes with Difluoroacetic Acid DOI
Claudio F. Meyer, Sandrine M. Hell,

Antonio Misale

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(26), P. 8829 - 8833

Published: April 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.

Language: Английский

Citations

135
Arenesulfonyl Fluoride Synthesis via Copper-Catalyzed Fluorosulfonylation of Arenediazonium Salts DOI
Yongan Liu, Donghai Yu,

Yong Guo

et al.

Organic Letters, Journal Year: 2020, Volume and Issue: 22(6), P. 2281 - 2286

Published: March 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.

Language: Английский

Citations

111