2.9 Fluorination Enabled by Photoredox Reactions DOI
Takashi Koike

Published: Jan. 1, 2024

Abstract In recent years, photoredox catalysis has become a useful strategy in the field of synthetic chemistry because generation reactive radicals, ionic species, and organometallics under mild reaction conditions can be realized. This review mainly discusses fluorination reactions carbon skeletons using catalysis. addition, seminal works on photochemical hydrogen-atom transfer (HAT) photocatalyst-free photoinduced electron-transfer systems are also handled. These applied to C—H bonds, C—C C=C appropriate functional groups.

Language: Английский

Picking Two out of Three: Defluorinative Annulation of Trifluoromethyl Alkenes for the Synthesis of Monofluorinated Carbo‐ and Heterocycles DOI
Jiahao Ling, Lei Zhou

The Chemical Record, Journal Year: 2024, Volume and Issue: 24(3)

Published: Jan. 22, 2024

Abstract The increasing demand of organofluorine compounds in medicine, agriculture, and materials sciences makes sophisticated methods for their synthesis ever more necessary. Nowadays, not only the C−F bond formation but also selective cleavage readily available poly‐ or perfluorine‐containing have become powerful tools effective compounds. defluorinative cross‐coupling trifluoromethyl alkenes with various nucleophiles radical precursors an S N 2’ manner is a convergent route to access gem ‐difluoroalkenes, which turn react via V‐type reaction. If V reactions occur intramolecularly, dual allows facile assembly monofluorinated cyclic skeletons structural complexity diversity. In this personal account, we summarized advances field on basis coupling cyclization partners, including binucleophiles, alkynes, diradical bearing nucleophilic site. Accordingly, annulation can be achieved by base‐mediated sequential 2′/S reactions, transition metal catalyzed mediated photoredox catalysis, combination photocatalytic context seminal works others field, concise summary contributions authors offered.

Language: Английский

Citations

10
Electrochemical or Photoelectrochemical Alkenylpolyfluoroalkylation of 3-Aza-1,5-dienes: Regioselective Entry to Polyfluoroalkylated 4-Pyrrolin-2-ones DOI
Xi Hu,

Minglin Tao,

Kaixing Gong

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(18), P. 12935 - 12948

Published: Sept. 6, 2023

An electrochemical or photoelectrochemical regioselective polyfluoroalkylation/cyclization cascade of 3-aza-1,5-dienes with sodium fluoroalkanesulfinates is presented. This protocol proceeds a broad substrate scope and good functional group tolerance under mild, oxidant-free, transition-metal-free, electrolyte-free conditions to provide 3-polyfluoroalkylated 4-pyrrolin-2-ones in one step from readily available N-vinylacrylamides, it scalable the Gram scale.

Language: Английский

Citations

15
Silver-Catalyzed Decarboxylative Remote Fluorination via a Zwitterion-Promoted 1,4-Heteroaryl Migration DOI
Xiaofei Xie, Jie Li, Weinan Li

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2228 - 2232

Published: March 8, 2024

A silver-catalyzed decarboxylative remote fluorination via a zwitterion-promoted 1,4-heteroaryl migration has been developed. variety of heteroaryl-tethered benzyl fluorides have readily synthesized with good regioselectivity under mild conditions. The zwitterion the substrate is suggested to accelerate migration, which determines this transformation.

Language: Английский

Citations

4
Catalytic Atroposelective aza-Grob Fragmentation: An Approach toward Axially Chiral Biarylnitriles DOI
Lin Li,

Linlin Ding,

Xue Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 6, 2025

Grob fragmentation is a powerful synthetic tool for cleaving C-C bonds, which was particularly useful in the construction of seven- to nine-membered carbocycles or heterocycles. This reaction typically breaks one bond and C-X forms two unsaturated functional groups. As no stereogenic centers are generated, catalytic asymmetric has remained unexplored. In this study, we have successfully developed aza-Grob α-keto oxime esters, achieving atroposelective cleavage construct axially chiral biarylnitriles. Single-crystal X-ray diffraction analysis esters elucidated structure-reactivity relationship, highlighting role torsional strain. These studies also revealed unique 2-phenyl benzoyl group controlling substrate conformation, tuning reactivity, stereoselectivity. The 1H NMR titration experiments provided brief insights into activation mode catalyst with substrate, suggesting multi-hydrogen-bonding interaction model.

Language: Английский

Citations

0
Visible Light-Promoted Aromatization-Driven Deconstructive Fluorination of Spiro Carbocycles DOI

Wenpeng Yang,

Hong-Jie Miao,

Le Liu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(35), P. 7442 - 7446

Published: Aug. 26, 2024

A visible light-promoted aromatization-driven deconstructive fluorination of spiro carbocycles is presented. series dihydroquinazolinones reacted efficiently with NFSI under light irradiation to afford the 2-(4-fluoroalkyl)quinazolin-4(3H)-ones in good yields excellent functional group tolerance. radical pathway involving C–C bond cleavage and F atom transfer proposed for reaction. In addition, ring-opening chlorination NCS was also applicable.

Language: Английский

Citations

2
A Strategic Synthesis of Fluoroethers via Ring-Opening Fluorinative Beckmann Fragmentation DOI

Chae Yeon Lee,

Su Eun Lee,

Hee Nam Lim

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(35), P. 6534 - 6538

Published: Aug. 24, 2023

An SN1-type fluorination method for monofluoroethers is developed. The key to this reaction fluorinative C–C bond cleavage that driven by oxygen-assisted Beckmann fragmentation. To enable transformation, cyclic α-aryloxyoximes derived from 3-coumaranone and 1-indanones were investigated as substrates, using N,N-diethylaminosulfur trifluoride (DAST) a dual-role reagent of an oxime activator fluoride donor. This features the synthesis underdeveloped chemical motif with simple mild operating conditions.

Language: Английский

Citations

4
Difluoroenoxysilanes in Catalytic Asymmetric Allylic Alkylation DOI
Subhajit Mondal, Priyotosh Das, Santanu Mukherjee

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 4, 2024

An allylic substitution with difluoroenoxysilanes as the nucleophile is accomplished for enantioselective synthesis of α-allylic α,α-difluoroketones. With racemic branched alcohols easily accessible electrophile, this branched-selective and enantioconvergent alkylation reaction catalyzed by an Ir(I)/(

Language: Английский

Citations

0
Ring-opening Difluorination of Pyrazoloazines DOI Creative Commons

Hugo Ohki,

Masaaki Komatsuda, Hiroki Kondo

et al.

Tetrahedron, Journal Year: 2024, Volume and Issue: 159, P. 134020 - 134020

Published: May 3, 2024

We have developed a novel ring-opening difluorination process for pyrazoloazines. Utilizing 2.5 equivalents of Selectfluor®, this method enables electrophilic and subsequent pyrazoloazines, yielding the corresponding difluoroalkylated azines. Additionally, our protocol extends to decarbonylative pyrazoloazines when starting with formyl group at C3 position, demonstrating versatility broad applicability approach. This advancement in chemistry offers new pathway synthesis difluorinated compounds, potentially enriching toolkit practitioners medicinal materials science.

Language: Английский

Citations

0
2.9 Fluorination Enabled by Photoredox Reactions DOI
Takashi Koike

Published: Jan. 1, 2024

Abstract In recent years, photoredox catalysis has become a useful strategy in the field of synthetic chemistry because generation reactive radicals, ionic species, and organometallics under mild reaction conditions can be realized. This review mainly discusses fluorination reactions carbon skeletons using catalysis. addition, seminal works on photochemical hydrogen-atom transfer (HAT) photocatalyst-free photoinduced electron-transfer systems are also handled. These applied to C—H bonds, C—C C=C appropriate functional groups.

Language: Английский

Citations

0