Access to Trifluoromethylketones from Alkyl Bromides and Trifluoroacetic Anhydride by Photocatalysis DOI

Hai‐Wu Du,

Yi‐Dan Du,

Xian‐Wang Zeng

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(38)

Published: Aug. 3, 2023

Abstract Aliphatic trifluoromethyl ketones are a type of unique fluorine‐containing subunit which play significant role in altering the physical and biological properties molecules. Catalytic methods to provide direct access aliphatic highly desirable yet remain underdeveloped, partially owing high reactivity instability trifluoroacetyl radical. Herein, we report photocatalytic synthesis from alkyl bromides with trifluoroacetic anhydride. The reaction features dual visible‐light halogen‐atom‐transfer catalysis, followed by an enabling radical‐radical cross‐coupling radical stabilized provides straightforward readily available cost‐effective halides anhydride (TFAA).

Language: Английский

Access to Trifluoromethylketones from Alkyl Bromides and Trifluoroacetic Anhydride by Photocatalysis DOI

Hai‐Wu Du,

Yi‐Dan Du,

Xian‐Wang Zeng

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: Aug. 3, 2023

Aliphatic trifluoromethyl ketones are a type of unique fluorine-containing subunit which play significant role in altering the physical and biological properties molecules. Catalytic methods to provide direct access aliphatic highly desirable yet remain underdeveloped, partially owing high reactivity instability trifluoroacetyl radical. Herein, we report photocatalytic synthesis from alkyl bromides with trifluoroacetic anhydride. The reaction features dual visible-light halogen-atom-transfer catalysis, followed by an enabling radical-radical cross-coupling radical stabilized provides straightforward readily available cost-effective halides anhydride (TFAA).

Language: Английский

Citations

16
Photoredox Enabled Defluorinative Benzylation of Trifluoromethyl Alkenes with Alkylarenes DOI

Yutao Shi,

Jinhuan Nie,

Zhijie Wu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 26(1), P. 100 - 105

Published: Dec. 26, 2023

Herein, we report a photoredox enabled defluorinative benzylation of trifluoromethyl alkenes with readily available alkylarenes, which provides convenient access to series structurally valuable benzylated gem-difluoroalkenes under mild reaction conditions. The synthetic value this protocol has been demonstrated by the transformations several substrates bearing drug moieties, gram-scale reactions, and various further derivatizations gem-difluoroalkene products. preliminary mechanistic investigations suggest pathway rate-determining benzyl C–H bond cleavage toluene followed benzylic radical formation.

Language: Английский

Citations

13
Visible light-induced bromine radical enhanced hydrogen atom transfer (HAT) reactions in organic synthesis DOI Creative Commons

Barakha Saxena,

Roshan I. Patel,

Anuj Sharma

et al.

RSC Sustainability, Journal Year: 2024, Volume and Issue: 2(8), P. 2169 - 2189

Published: Jan. 1, 2024

This review describes the recent advancements in visible light-induced bromine radical enhanced hydrogen atom transfer (HAT) reactions organic synthesis.

Language: Английский

Citations

5
Electrochemical Oxidative Carbonylation of NH-Sulfoximines DOI
Mingzhe Li,

Mengyu Peng,

Wenxiu Huang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(41), P. 7529 - 7534

Published: Oct. 11, 2023

The electrochemical synthesis of N-aroylsulfoximines features the use tetra-n-butylammonium iodide (TBAI) as medium and a broad substrate scope, thus affording wide range N-aroylated sulfoximines in moderate to good yields. advantages this strategy are augmented by mild reaction conditions that external oxidant-free, ligand-free, easy scale up gram scale. Both control experiments mechanistic studies revealed whole process proceeded through palladium (II/IV/II) catalytic cycle.

Language: Английский

Citations

11
Redox-Neutral Cyclization of 2-Isocyanobiaryls through Photoredox/PPh3 Dual Catalysis DOI
Xiaoting Wu, Pu Chen,

Mengran Gan

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(51), P. 9186 - 9190

Published: Dec. 15, 2023

The photoredox/PPh3-mediated cyclization of 2-isocyanobiaryls has been developed. A substantial range functional-group-rich phenanthridine derivatives were synthesized at room temperature in a highly selective and atom-economic manner. Mechanistic studies suggested that the process is probably mediated both by Ph3P radical cation with key 1,2-hydride transfer hydrogen atom generated through O–H bond homolytic cleavage Ph3P–OH intermediate.

Language: Английский

Citations

11
Thiobenzoic Acid-Catalyzed Cα–H Cross Coupling of Benzyl Alcohols with α-Ketoacid Derivatives DOI

Kaichi Sato,

Hiromichi Egami, Yoshitaka Hamashima

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(25), P. 5285 - 5289

Published: June 13, 2024

The C-H alkylation of benzyl alcohols with α-ketoacid derivatives was achieved in the presence thiobenzoic acid or without Ru Ir photoredox catalysts. serves as a photoexcited single-electron reducing reagent and hydrogen atom transfer catalyst, while addition metal catalyst assists electron improves reaction efficiency. Various functional groups were tolerant conditions, sterically hindered diols produced good to high yield.

Language: Английский

Citations

4
Green and sustainable site- and cross-selective C-H reductive coupling of para-quinone methides with quinoxaline-2(1H)-ones DOI Creative Commons
Chuan‐Hua Qu, Sisi Zhang,

Hongbo Peng

et al.

Green Synthesis and Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

Citations

0
General Defluoroalkylation of Trifluoromethylarenes with Both Electron-Donating and -Withdrawing Alkenes DOI
Mengqi Zhu, Qiaolin Wang, Huawen Huang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12591 - 12609

Published: Aug. 14, 2024

The incorporation of gem-difluoromethylene units into organic molecules remains a formidable challenge. Conventional methodologies for constructing aryldifluoromethyl derivatives relied on the use high-functional fluorinating regents under harsh conditions. Herein, we report general and efficient photoredox catalytic systems defluoroalkylation readily available trifluoromethylarenes through selective C–F cleavage to deliver gem-difluoromethyl radicals which proceed reductive addition both electron-donating withdrawing alkenes transition-metal free Mechanistic studies reveal that thiol serves as photocatalyst HAT reagent visible light irradiation. This synergistic photocatalysis catalysis protocol exhibits ample salient features such high chemo- regioselectivity, broad substrate scope, amenable gram-scale synthesis late-stage modification bioactive molecules.

Language: Английский

Citations

2
Synthesis of Oxazoles Containing CF3-Substituted Alcohol Unit via Tandem Cycloisomerization/Hydroxyalkylation from N-Propargylamides with Trifluoropyruvates DOI Creative Commons
Juanjuan Gao,

Longhui Wu,

Shuqin Yu

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(24), P. 5848 - 5848

Published: Dec. 11, 2024

Oxazoles are important five-membered heterocycles that contain both nitrogen and oxygen atoms. Due to their wide range of biological activities, many oxazoles demonstrate potential for extensive application in various fields, including medicinal chemistry. Trifluoromethyl carbinol, an pharmacophore, contains trifluoromethyl hydroxyl groups is common molecules with activities. Constructing a carbinol unit undoubtedly valuable expanding the chemical space drug discovery. In this study, simple efficient method was developed synthesis containing CF3-substituted alcohol via tandem cycloisomerization/hydroxyalkylation N-propargylamides trifluoropyruvates through rational Lewis acid catalytic mechanism. This Zn(OTf)2-catalyzed synthetic protocol operationally provides series moderate good yields. The demonstrates broad substrate scope, high functional group tolerance, atom economy can achieve gram-level reactions, indicating strong possibility its practical application.

Language: Английский

Citations

1
Diastereoselective Construction of α‐Fluoroalkyl Cycloalkanols via Radical Alkylation of α‐Fluoroalkyl Ketones† DOI
Yi Liu, Ji Li, Yulu Zhou

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(23), P. 3275 - 3280

Published: July 27, 2023

Comprehensive Summary α‐Fluoroalkyl (R f ) alcohols are privileged motifs in drugs and pharmaceutically active compounds. As such, it is highly desirable to develop efficient methods for assembling these scaffolds. Herein, a visible‐light‐induced cascade radical cyclization of alkenyl fluoroalkyl ketones developed, producing variety decorate α‐R cycloalkanols promising yields with up >20 : 1 dr selectivity. A chain mechanism involving an intramolecular addition the carbonyl group subsequent intermolecular hydrogen atom transfer (HAT) has been proposed. Density functional theory (DFT) calculations indicate that fluorine effect contributes carbonyls by lowering π* (C=O) orbital energy COR barrier HAT between alkoxy radicals THF, which may be valuable controllable transformations fluorinated molecules.

Language: Английский

Citations

3