Transition metal-free photochemical C–F activation for the preparation of difluorinated-oxindole derivatives DOI Creative Commons
Bianca T. Matsuo, Jadab Majhi, Albert Granados

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(9), P. 2379 - 2385

Published: Jan. 1, 2023

The development of strategies for single and selective C-F bond activation represents an important avenue to overcome limitations in the synthesis valuable fluorine-containing compounds. synthetic medicinal research communities would benefit from new routes that access such relevant molecules a simple manner. Herein we disclose straightforward mechanistically distinct pathway generate gem-difluoromethyl radicals their installation onto N-arylmethacrylamides preparation difluorinated oxindole derivatives. To achieve operational simplicity, use readily available benzenethiol as photocatalyst under open-to-air conditions was developed, demonstrating facile multigram targeted fluorinated molecules. Additionally, dispersion-corrected density functional theory (DFT) empirical investigations provide basis support proposed reaction pathway, indicating arene thiolate is efficient organophotocatalyst this transformation.

Language: Английский

Construction of C–X (X = S, O, Se) Bonds via Lewis Acid-Promoted Functionalization of Trifluoromethylarenes DOI
Jun Xu, Jiawei Liu,

Rui Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(11), P. 7339 - 7346

Published: May 16, 2023

The conversion of easily available trifluoromethylarenes through C–F bond activation provides an attractive pathway for rapid access to difluorobenzylic substructures in producing pharmaceuticals and agrochemicals. However, recent advances this area have been confined C–C(H) construction, thus limiting the diversity accessible motifs. In contrast, selective formation a carbon–heteroatom via functionalization, which enable fast convenient diverse fluorine-containing motifs with high chemical diversity, remains formidable synthetic challenge. Herein, we disclosed Lewis acid promoted photoredox-catalyzed strategy construction C–X (X = S, O or Se) bonds by single C(sp3)–F trifluoromethylarenes, direct synthesis medicinally interesting aryldifluoromethyl ether [ArCF2X– O, Se)] scaffolds. This method relies on readily reagents can tolerate range thiol, phenol, selenol nucleophiles. Its utility was exemplified late-stage modifications several pharmaceutical ingredients. Preliminary studies suggest two parallel pathways: photocatalytic electron-transfer (SET), electron donor–acceptor (EDA) process.

Language: Английский

Citations

33
Aminals as powerful XAT-reagents: activation of fluorinated alkyl chlorides DOI Creative Commons

Vladislav S. Kostromitin,

Artem O. Sorokin,

Vitalij V. Levin

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(12), P. 3229 - 3234

Published: Jan. 1, 2023

Reagents for the activation of C–Cl bond via XAT process are described. The reaction efficiency is based on stereoelectronic effects. method applied to chlorofluorocarbons.

Language: Английский

Citations

32
Regiodivergent electroreductive defluorinative carboxylation ofgem-difluorocyclopropanes DOI
Bin Zhao,

Zichen Pan,

Jiayu Pan

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(8), P. 3095 - 3102

Published: Jan. 1, 2023

A regiodivergent electrochemical defluorocarboxylation of gem -difluorocyclopropanes is realized, providing access to branched and linear carboxylated monofluorinated alkenes.

Language: Английский

Citations

29
Recent Advances in C–H Functionalisation through Indirect Hydrogen Atom Transfer DOI Creative Commons
Filip S. Meger, John A. Murphy

Molecules, Journal Year: 2023, Volume and Issue: 28(16), P. 6127 - 6127

Published: Aug. 18, 2023

The functionalisation of C–H bonds has been an enormous achievement in synthetic methodology, enabling new retrosynthetic disconnections and affording simple equivalents for synthons. Hydrogen atom transfer (HAT) is a key method forming alkyl radicals from substrates. Classic reactions, including the Barton nitrite ester reaction Hofmann–Löffler–Freytag reaction, among others, provided early examples HAT. However, recent developments photoredox catalysis electrochemistry have made HAT powerful tool capable introducing wide range functional groups into bonds. Moreover, greater mechanistic insights stimulated development increasingly site-selective protocols. Site-selectivity can be achieved through tuning electron density at certain using additives, judicious choice reagent, solvent system. Herein, we describe latest methods functionalizing C–H/Si–H/Ge–H indirect between 2018–2023, as well critical discussion reagents, aspects, substrate scopes, background contexts

Language: Английский

Citations

29
Transition metal-free photochemical C–F activation for the preparation of difluorinated-oxindole derivatives DOI Creative Commons
Bianca T. Matsuo, Jadab Majhi, Albert Granados

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(9), P. 2379 - 2385

Published: Jan. 1, 2023

The development of strategies for single and selective C-F bond activation represents an important avenue to overcome limitations in the synthesis valuable fluorine-containing compounds. synthetic medicinal research communities would benefit from new routes that access such relevant molecules a simple manner. Herein we disclose straightforward mechanistically distinct pathway generate gem-difluoromethyl radicals their installation onto N-arylmethacrylamides preparation difluorinated oxindole derivatives. To achieve operational simplicity, use readily available benzenethiol as photocatalyst under open-to-air conditions was developed, demonstrating facile multigram targeted fluorinated molecules. Additionally, dispersion-corrected density functional theory (DFT) empirical investigations provide basis support proposed reaction pathway, indicating arene thiolate is efficient organophotocatalyst this transformation.

Language: Английский

Citations

28