Organic Letters, Год журнала: 2023, Номер 25(43), С. 7816 - 7821
Опубликована: Окт. 23, 2023
An electrochemical strategy for the decarboxylative elimination of carboxylic acids to alkenes at room temperature has been developed. This mild and oxidant-free method provides a green alternative traditional thermal decarboxylation reactions. Structurally diverse aliphatic acids, including biologically active drugs, underwent smooth conversion corresponding in good excellent yields.
Язык: Английский
European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(21)
Опубликована: Апрель 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.
Язык: Английский
Процитировано
57
Organic Letters, Год журнала: 2022, Номер 24(32), С. 5972 - 5976
Опубликована: Авг. 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.
Язык: Английский
Процитировано
68
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)
Опубликована: Апрель 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.
Язык: Английский
Процитировано
36
Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(19), С. 4764 - 4773
Опубликована: Янв. 1, 2023
A photo-induced iron-catalyzed strategy that facilitates the transformation of carboxylic acids and hydrocarbons into thioethers sulfoxides is herein reported.
Язык: Английский
Процитировано
31
ACS Catalysis, Год журнала: 2024, Номер 14(15), С. 11308 - 11317
Опубликована: Июль 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).
Язык: Английский
Процитировано
14
Tetrahedron, Год журнала: 2025, Номер unknown, С. 134545 - 134545
Опубликована: Март 1, 2025
Язык: Английский
Процитировано
1
Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(7)
Опубликована: Окт. 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.
Язык: Английский
Процитировано
56
The Chemical Record, Год журнала: 2022, Номер 22(5)
Опубликована: Март 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.
Язык: Английский
Процитировано
35
Chinese Chemical Letters, Год журнала: 2022, Номер 34(1), С. 107473 - 107473
Опубликована: Апрель 30, 2022
Язык: Английский
Процитировано
30
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(12)
Опубликована: Янв. 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.
Язык: Английский
Процитировано
19