Ring‐Opening Fluorination of Carbo/Heterocycles and Aromatics: Construction of Complex and Diverse Fluorine‐Containing Molecules DOI
Masaaki Komatsuda, Junichiro Yamaguchi

The Chemical Record, Journal Year: 2023, Volume and Issue: 23(9)

Published: Jan. 5, 2023

Abstract Fluorine‐containing molecules have attracted much attention in medicinal, agrochemical, and materials sciences because they offer unique physical biological properties. Therefore, many efficient fluorination reactions been developed over the years. Recent advancements chemistry expanded range of substrates, regioselectivity/stereoselectivity control has also achieved. Ring‐opening is an method to construct complex fluorine‐containing with diversity, starting from simple cyclic compounds. This review aims summarize developments ring‐opening fluorination, particularly larger‐sized Fluorine introduction bond cleavage compounds such as carbocycles, heterocycles, aromatics provide access that are difficult be synthesized by conventional methods.

Language: Английский

Synthetic Advantages of Defluorinative C−F Bond Functionalization DOI Creative Commons
Leidy V. Hooker, Jeffrey S. Bandar

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Aug. 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.

Language: Английский

Citations

57
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
Hydrogen Bonding Phase-Transfer Catalysis with Alkali Metal Fluorides and Beyond DOI Creative Commons
Gabriele Pupo, Véronique Gouverneur

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(12), P. 5200 - 5213

Published: March 16, 2022

Phase-transfer catalysis (PTC) is one of the most powerful catalytic manifolds for asymmetric synthesis. Chiral cationic or anionic PTC strategies have enabled a variety transformations, yet studies on use insoluble inorganic salts as nucleophiles synthesis enantioenriched molecules remained elusive. A long-standing challenge development methods carbon-fluorine bond formation from readily available and cost-effective alkali metal fluorides. In this Perspective, we describe how H-bond donors can provide solution through fluoride binding. We examples, primarily our own research, to discuss hydrogen bonding interactions impact reactivity role phase-transfer catalysts bring solid-phase fluorides in solution. These led (HB-PTC), new concept PTC, originally crafted but offering opportunities beyond enantioselective fluorination. Looking ahead, unlimited options that consider diversify donor, salt, electrophile, herald era catalysis. Whether abundant lattice energy significantly higher than those studied date could be considered nucleophiles, e.g., CaF2, remains an open question, with solutions may found synergistic PTC.

Language: Английский

Citations

50
Photocatalytic Decarboxylative Fluorination by Quinone-Based Isoreticular Covalent Organic Frameworks DOI
Ayan Jati, Ashok Kumar Mahato,

Durba Chanda

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(34), P. 23923 - 23932

Published: Aug. 16, 2024

The strategic incorporation of fluorine atoms into molecules has become a cornerstone modern pharmaceuticals, agrochemicals, and materials science. Herein, we have developed covalent organic framework (COF)-based, robust photocatalyst that enables the photofluorodecarboxylation reaction diverse carboxylic acids, producing alkyl fluorides with remarkable efficiency. catalytic activity an anthraquinone-based COF catalyst

Language: Английский

Citations

11
Development of N-F fluorinating agents and their fluorinations: Historical perspective DOI Creative Commons
Teruo Umemoto, Yuhao Yang, Gerald B. Hammond

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 17, P. 1752 - 1813

Published: July 27, 2021

This review deals with the historical development of all N -F fluorinating agents developed so far. The unique properties fluorine make fluorinated organic compounds attractive in many research areas and therefore are important. have proven useful by virtue their easy handling. reagent class includes types compounds: perfluoro- -fluoropiperidine, -fluoro-2-pyridone, -fluoro- -alkylarenesulfonamides, -fluoropyridinium salts derivatives, -fluoroquinuclidium salts, -fluoro-trifluoromethanesulfonimide, -fluoro-sultams, -fluoro-benzothiazole dioxides, -fluoro-lactams, o -benzenedisulfonimide, -fluoro-benzenesulfonimide, 1-alkyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane -fluoropyridinium-2-sulfonate 1-fluoro-4-hydroxy-1,4-diazoniabicyclo[2.2.2]octane -fluorodinitroimidazole, -fluoro-trichloro-1,3,5-triazinium salt, ethano-Tröger’s base -fluoro-methanesulfonimide, -arylarenesulfonamides, bis such as , N’ -difluorobipyridinium -difluoro-1,4-diazoniabicyclo[2.2.2]octane derivatives analogs, including chiral reagents optically active -fluoro-sultam -fluoro-alkaloid DABCO-based binaphthyldisulfonimides. synthesis reactions these described chronologically also discusses relative fluorination power each mechanisms chronicling developments from a perspective.

Language: Английский

Citations

51
Closing the gap between 19F and 18F chemistry DOI Creative Commons
Javier Ajenjo, Gianluca Destro, Bart Cornelissen

et al.

EJNMMI Radiopharmacy and Chemistry, Journal Year: 2021, Volume and Issue: 6(1)

Published: Sept. 25, 2021

Abstract Positron emission tomography (PET) has become an invaluable tool for drug discovery and diagnosis. The positron-emitting radionuclide fluorine-18 is frequently used in PET radiopharmaceuticals due to its advantageous characteristics; hence, methods streamlining access 18 F-labelled radiotracers can make a direct impact medicine. For many years, was limited by the paucity of methodologies available, poor diversity precursors amenable F-incorporation. During last two decades, F-radiochemistry progressed at fast pace with appearance numerous late-stage F-incorporation onto complex molecules from range readily available including those that do not require pre-functionalisation. Key these advances inclusion new activation modes facilitate Specifically, 19 F-fluorination under transition metal catalysis, photoredox organocatalysis combined availability novel fluorination reagents have enabled invention processes (bio)molecules. This review describes major breakthroughs focus on C– F bond formation. reinvigorated interest we witnessed recent years made F-chemistry laboratories refocusing their efforts development using nucleophilic fluoride instead derived molecular fluorine gas.

Language: Английский

Citations

49
Mechanism of the Aryl–F Bond-Forming Step from Bi(V) Fluorides DOI
Oriol Planas, Vytautas Pečiukėnas, Markus Leutzsch

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(32), P. 14489 - 14504

Published: Aug. 3, 2022

In this article, we describe a combined experimental and theoretical mechanistic investigation of the C(sp

Language: Английский

Citations

32
Copper-Catalyzed Three-Component Aminofluorination of Alkenes and 1,3-Dienes: Direct Entry to Diverse β-Fluoroalkylamines DOI
Guang‐Shou Feng,

Colton K. Ku,

Jiaqi Zhao

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(44), P. 20463 - 20471

Published: Oct. 24, 2022

Rapid and efficient access to structurally diverse β-fluoroalkylamines is in high demand, with their wide presence great importance medicinal chemistry drug development. Direct 1,2-aminofluorination of alkenes offers an ideal strategy for one-step entry β-fluorinated amines from readily available starting materials. Yet the synthesis valuable alkylamines remains unsolved challenge, due inherent incompatibility between electrophilic fluoride sources electron-rich alkylamines. We report unprecedented, catalytic, three-component aminofluorination 1,3-dienes, which has been achieved by innovative copper-catalyzed amination using O-benzoylhydroxylamines as alkylamine precursors. The use Et3N·3HF also critical, not only a commercially inexpensive source enable effective fluorination but acid formation aminyl radical cations amination. Mechanistic experiments suggest involvement species carbon-radical intermediates under reaction conditions. This method features regioselectivity good tolerance functional groups provides practical direct broad range Synthetic applications this have highlighted its rapid β-fluoridated amine-containing pharmaceuticals, natural products, bioactive compounds.

Language: Английский

Citations

29
Chiral Bis‐phosphate Macrocycles for Catalytic, Efficient, and Enantioselective Electrophilic Fluorination DOI

Lie‐Wei Zhang,

Wang Xu-dong, Yu‐Fei Ao

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(24)

Published: Feb. 21, 2024

Incorporation of privileged catalytic scaffolds into a macrocyclic skeleton represents an attractive strategy to furnish supramolecular catalysis systems with enzyme-mimetic cavity and multi-site cooperation. Herein we reported the synthesis, structure, binding properties application series chiral bis-phosphate macrocycles toward challenging asymmetric electrophilic fluorination. With large, integrated two cooperative phosphate sites, these exhibited good inclusion 1,4-diazabicyclo[2.2.2]octane (DABCO) dicationic ammoniums through complementary ion-pair C-H⋅⋅⋅O interactions, as confirmed by crystallographic solution studies. In fluorocyclization tryptamines Selectfluor reagent which has similar DABCO-based only 2 mol% macrocycle catalyst afforded desired pyrroloindoline products in moderate yields up 91 % ee. For comparison, acyclic mono-phosphate analogue gave obviously lower reactivity enantioselectivity (<20 ee), suggesting remarkable effect. The high efficiency superior stereocontrol were ascribed tight cavity-directed noncovalent interaction

Language: Английский

Citations

6
Cobalt-Catalyzed Divergent Aminofluorination and Diamination of Styrenes with N-Fluorosulfonamides DOI
Peng Guo,

Jun‐Fa Han,

Guo-Cai Yuan

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(10), P. 4067 - 4071

Published: May 10, 2021

A cobalt-catalyzed aminofluorination reaction of styrenes with N-fluorosulfonamides serving as both the amination and fluorination agents has been developed. The switch selectivity in this catalytic from to diamination could be easily achieved by addition 1.0 equiv PPh3. Both transformations tolerated a wide array substrates under mild conditions.

Language: Английский

Citations

38