Nitrogen-Based Organofluorine Functional Molecules: Synthesis and Applications DOI
Shuai Liu, Jun Zhou, Lu Yu

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

Fluorine and nitrogen form a successful partnership in organic synthesis, medicinal chemistry, material sciences. Although fluorine-nitrogen chemistry has long rich history, this field received increasing interest made remarkable progress over the past two decades, driven by recent advancements transition metal organocatalysis photochemistry. This review, emphasizing contributions from 2015 to 2023, aims update state of art synthesis applications nitrogen-based organofluorine functional molecules chemistry. In dedicated sections, we first focus on fluorine-containing reagents organized according type groups attached nitrogen, including N-F, N-RF, N-SRF, N-ORF. review also covers nitrogen-linked building blocks, catalysts, pharmaceuticals, agrochemicals, underlining these components' broad applicability growing importance modern

Language: Английский

Free Carboxylic Acids: The Trend of Radical Decarboxylative Functionalization DOI
Liubo Li, Yan Yao, Niankai Fu

et al.

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(21)

Published: April 7, 2023

Abstract The exceptional versatility of carboxylic acids has been extensively exploited in organic synthesis across several decades. There a recent upsurge radical decarboxylative transformations. process can be initiated under mild conditions, and the resultant radicals have orthogonal reactivities to closed‐shell species, thus providing immense opportunities for streamlining novel reactions. use free is most desirable owing its high atom step economy. Aiming demonstrate attractiveness strategy inspire chemists tackle existing challenges, this review outlines advances on functionalization acids.

Language: Английский

Citations

54
Visible-Light-Induced Decarboxylative Fluorination of Aliphatic Carboxylic Acids Catalyzed by Iron DOI
Yu Zhang, Jiahui Qian, Miao Wang

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(32), P. 5972 - 5976

Published: Aug. 11, 2022

An efficient and inexpensive protocol for the direct decarboxylative fluorination of aliphatic carboxylic acids catalyzed with iron salts under visible light is presented. This new method allows facile a diverse array even on gram scale using Schlenk flask without loss efficiency. Mechanistic studies suggest that photoinduced ligand-to-metal charge transfer process enables generation key step to generate carboxyl radical intermediates.

Language: Английский

Citations

67
Chemo‐, Stereo‐ and Regioselective Fluoroallylation/Annulation of Hydrazones with gem‐Difluorocyclopropanes via Tunable Palladium/NHC Catalysis DOI
Huijun Qian,

Hieu D. Nguyen,

Leiyang Lv

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: April 4, 2023

Defluorinative manipulation of polyfluorinated molecules has shown great promise due to its granting synthetic versatility inert C-F bonds. The development chemo-, stereo- and regioselective strategies realize highly efficient formation either the linear/branched or E/Z products from gem-difluorocyclopropanes (gem-F2 CPs) is a challenging task. Herein, we have realized palladium/NHC-catalyzed fluoroallylation/annulation hydrazones with gem-F2 CPs that incorporate hydrazone N2 moiety into products. thermodynamically unstable fluorinated E-allylation aryl ketone were obtained for first time, while di-alkyl yielded monofluorinated branched selectivity under similar reaction conditions. With aldehyde hydrazones, two kinds pyrazoles via defluorinative allylation/annulation cascade, in which different carbon atoms could be incorporated pyrazole rings regiospecifically. DFT calculations revealed divergent was kinetically controlled final C-C bond proceeded through 7-membered TS.

Language: Английский

Citations

36
An iron-catalyzed C–S bond-forming reaction of carboxylic acids and hydrocarbons via photo-induced ligand to metal charge transfer DOI

Ao-Men Hu,

Jia‐Lin Tu,

Mengqi Luo

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(19), P. 4764 - 4773

Published: Jan. 1, 2023

A photo-induced iron-catalyzed strategy that facilitates the transformation of carboxylic acids and hydrocarbons into thioethers sulfoxides is herein reported.

Language: Английский

Citations

28
Enhancing Photocatalytic Redox Activity of Polymeric Carbon Nitride for Valuable Fluorinated Heterocycles through Fast-Track Electron Highways DOI Creative Commons
Chong Wang, Shiru Lin, Yichun Lu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11308 - 11317

Published: July 15, 2024

The ionic structure of poly(heptazine imides) has a strong implication in photocatalytic hydrogen generation. From numerous reports, it is evident that these materials are also superior to covalent carbon nitrides various organic transformations. However, the reason been remaining vague. Herein, we report design molten-salt nitride (MCN) featuring represented by negatively charged polymeric scaffold and K+ counterions application this material as photocatalyst synthesis pharmaceutically relevant fluorinated heterocycles under visible light redox neutral conditions. ions serve sites for sorption ethyl bromodifluoroacetate, while electronically excited state MCN acts single electron transfer agent, enabling generation difluoroalkyl radicals from substrate. Combination two features endows outperforms homogeneous photocatalysts nitrides. Our protocol expands compounds with complex provides fresh perspectives on factors contributing enhanced efficiency imides).

Language: Английский

Citations

12
Transition‐Metal‐Catalyzed Monofluoroalkylation: Strategies for the Synthesis of Alkyl Fluorides by C−C Bond Formation DOI Creative Commons
Trevor W. Butcher, Willi M. Amberg, John F. Hartwig

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(7)

Published: Oct. 20, 2021

Abstract Alkyl fluorides modulate the conformation, lipophilicity, metabolic stability, and pKa of compounds containing aliphatic motifs and, therefore, have been valuable for medicinal chemistry. Despite significant research in organofluorine chemistry, synthesis alkyl fluorides, especially chiral remains a challenge. Most commonly, are prepared by formation C−F bonds (fluorination), numerous strategies nucleophilic, electrophilic, radical fluorination reported recent years. Although to access C−C bond (monofluoroalkylation) inherently convergent complexity‐generating, they studied less than methods based on fluorination. This Review provides an overview developments (enantioenriched or racemic) secondary tertiary monofluoroalkylation catalyzed transition‐metal complexes. We expect this contribution will illuminate potential monofluoroalkylations simplify complex suggest further directions growing field.

Language: Английский

Citations

54
Fluorinated Nucleosides: Synthesis, Modulation in Conformation and Therapeutic Application DOI
Shantanu Pal, Girish Chandra, Samridhi Patel

et al.

The Chemical Record, Journal Year: 2022, Volume and Issue: 22(5)

Published: March 7, 2022

Abstract Over the last twenty years, fluorination on nucleoside has established itself as most promising tool to use get biologically active compounds that could sustain clinical trial by affecting pharmacodynamics and pharmacokinetic properties. Due fluorine's inherent unique properties its judicious introduction into molecule, makes corresponding metabolically very stable, lipophilic, opens a new site of intermolecular binding. Fluorination various nucleosides been extensively studied result, series fluorinated come up for different therapeutic uses which are either approved FDA or under advanced stage trial. Here in this review, we summarizing latest development chemistry led varieties analogs like carbocyclic, acyclic, conformationally biased their biological properties, influence fluorine conformation, oligonucleotide stability, therapeutics.

Language: Английский

Citations

34
Visible-light-induced direct hydrodifluoromethylation of alkenes with difluoromethyltriphenylphosphonium iodide salt DOI Open Access

Xiaojian Ren,

Qiang Liu, Zhixiang Wang

et al.

Chinese Chemical Letters, Journal Year: 2022, Volume and Issue: 34(1), P. 107473 - 107473

Published: April 30, 2022

Language: Английский

Citations

30
Merging Copper(I) Photoredox Catalysis and Iodine(III) Chemistry for the Oxy‐monofluoromethylation of Alkenes DOI
Nagarajan Ramkumar,

Л. Баумане,

Dzintars Začs

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(12)

Published: Jan. 24, 2023

A simple process for the oxy-monofluoromethylation of alkenes is described. In combination with visible-light copper(I) photoredox catalysis, an easily accessible iodine(III) reagent containing monofluoroacetoxy ligands serves as a powerful source monofluoromethyl (CH2 F) radical, enabling step economical synthesis γ-fluoro-acetates from broad range olefinic substrates under mild conditions. Applications to late-stage diversification derived complex molecules, amino acids and fluoromethylated heterocycles are also demonstrated.

Language: Английский

Citations

18
General Approach to Amides through Decarboxylative Radical Cross-Coupling of Carboxylic Acids and Isocyanides DOI Creative Commons
Qing Yan,

Qing-Jia Yuan,

Andrey Shatskiy

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(16), P. 3380 - 3385

Published: April 12, 2024

Herein, we report a silver-catalyzed protocol for decarboxylative cross-coupling between carboxylic acids and isocyanides, leading to linear amide products through free-radical mechanism. The disclosed approach provides general entry variety of decorated amides, accommodating diverse array radical precursors, including aryl, heteroaryl, alkynyl, alkenyl, alkyl acids. Notably, the proved be efficient late-stage functionalization several elaborate pharmaceuticals, demonstrating its potential applications.

Language: Английский

Citations

8