Visible Light‐Induced Metal‐Free Fluoroalkylations

The Chemical Record, Год журнала: 2023, Номер 23(9)

Опубликована: Март 21, 2023

Abstract Fluoroalkylation is a crucial synthetic process that enables the modification of molecules with fluoroalkyl groups, which can enhance properties compounds and have potential applications in medicine materials science. The utilization visible light‐induced, metal‐free methods particular importance as it provides an environmentally friendly alternative to traditional eliminates risks associated metal‐catalyst toxicity. This Account describes our studies on fluoroalkylation processes, include use organic photocatalysts or EDA complexes. We utilized organophotocatalysts such Nile red, tri(9‐anthryl)borane, indole‐based tetracyclic complex, well catalyst‐free chemistry through photoactive halogen bond formation unconventional transient ternary complex nucleophilic source. A variety π‐systems including arenes/heteroarenes, alkenes, alkynes been successfully fluoroalkylated under developed reaction conditions.

Язык: Английский

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Nitro-Spirocyclization of Biaryl Ynones with tert-Butyl Nitrite: Access to NO₂-Substituted Spiro[5,5]trienones

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(7), С. 4854 - 4862

Опубликована: Март 22, 2023

A metal/peroxide-free involved simple cascade 6-exo-trig spirocyclization of tert-butyl nitrite with biaryl ynones has been finished, which resulted in various NO2-modified spiro[5,5]trienones good regioselectivity/yields. variety scaled-up experiments, reduction/epoxidation operations, and mechanistic studies were performed to verify the merits process this radical system. Finally, structure spirocycles was confirmed by single-crystal X-ray diffraction.

Язык: Английский

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External oxidant-free and selective thiofunctionalization of alkenes enabled by photoredox-neutral catalysis

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(17), С. 4536 - 4541

Опубликована: Янв. 1, 2022

A photoredox approach was reported to realize a highly selective three-component thiohydroxylation, thioalkoxylation and thioamination of vinylarenes towards valuable vicinal S,O - S,N -disubstituted molecules under mild conditions.

Язык: Английский

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Copper-assisted trifluoromethylthiolation/radical cascade cyclization of alkynes to construct SCF₃-containing dioxodibenzothiazepines

Chemical Communications, Год журнала: 2022, Номер 58(62), С. 8674 - 8677

Опубликована: Янв. 1, 2022

A mild and efficient Cu-assisted trifluoromethylthiolation/radical cascade cyclization of alkynes with readily available stable AgSCF3 as the trifluoromethylthiolating reagent has been disclosed. This transformation provides an opportunity to construct a series potential medicinally valuable trifluoromethylthio-substituted dioxodibenzothiazepines wide functional group compatibility. protocol opens up new avenue for construction useful trifluoromethylthiolated seven-membered N-heterocycles.

Язык: Английский

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Free Radical Promoted Trifluoromethylthiolation of Alkynes to Access SCF₃-Containing Dibenzazepines or Dioxodibenzothiazepines

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(13), С. 8773 - 8781

Опубликована: Июнь 16, 2022

Persulfate-promoted radical cascade trifluoromethylthiolation of aryl acetylenes with AgSCF3 provides a simple reaction system for the synthesis SCF3-substituted dibenzazepines or dioxodibenzothiazepines good Z/E selectivity. The single-crystal X-ray diffraction data confirms structures final products. A series scaled-up experiments, further transformations, and inhibition experiments were operated in system.

Язык: Английский

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Metal-Free Electrochemical Oxidative Difluoroethylation/Cyclization of Olefinic Amides To Construct Difluoroethylated Azaheterocycles

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(3), С. 1875 - 1883

Опубликована: Янв. 20, 2023

A new strategy of electrochemical oxidative difluoroethylation to generate difluoroethyl radical with sodium difluoroethylsulfinate (DFES-Na) has been reported for the first time. The method allows quick access a variety valuable difluoroethylated azaheterocycles including oxindoles and isoquinoline-1,3-diones via tandem difluoroethylation/cyclization in moderate good yields. cyclopropyldifluoromethylation N-arylacrylamides also works well using this strategy. Moreover, capture cyclic voltammetry (CV) experiments are carried out determine proposed mechanism.

Язык: Английский

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Visible-Light Photoredox Catalysis for the Synthesis of Fluorinated Aromatic Compounds

Catalysts, Год журнала: 2023, Номер 13(1), С. 94 - 94

Опубликована: Янв. 2, 2023

Fluorine-containing functional groups are important motifs influencing physical and biological properties of organic compounds. Visible-light photoredox catalysis as a powerful strategy for the activation small molecules contributed significantly to rapid progress new synthetic procedures allowing introduction fluorine atoms into substrates. In this review, we highlight distinct strategies transition metal- organic-photocatalytic fluorination arenes heteroarenes by broad range fluorinating The presented divided two groups. first group involves reactions enabling direct attachment CF3-, CnFm-, F-, CF3O-, CF3S-, SO2F- substituents various aromatic second presents tandem where formation system occurs after installation fluorine-containing on non-aromatic fragment molecule.

Язык: Английский

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Photoinduced Three‐Component Difluoroamidosulfonylation/Bicyclization: Regioselectivity Synthesis of Seven‐Membered Dibenzosultams

Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(10), С. 1750 - 1756

Опубликована: Апрель 1, 2022

Abstract A mild and safe photochemical methodology has been developed to access difluoroamidosulfonylated dioxodibenzothiazepines via three‐component radical bicyclization cascades. This photocatalyst‐free transformation avoids cumbersome photocatalyst removal procedure potential toxicity. Mechanistic experiments reveal the generation of an electron donor‐acceptor (EDA) complex in reaction process. Moreover, synthetic value protocol is further demonstrated by gram‐scale reaction, conversion product total synthesis antidepressant drug. magnified image

Язык: Английский

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Crystal structure of 2-chloro-11-(((fluoromethyl)sulfonyl)methyl)-6-methyl-6,11-dihydrodibenzo[c,f][1,2]thiazepine 5,5-dioxide, C₁₆H₁₃ClFNO₄S₂

Zeitschrift für Kristallographie - New Crystal Structures, Год журнала: 2025, Номер unknown

Опубликована: Апрель 23, 2025

Abstract C 16 H 13 ClFNO 4 S 2 , monoclinic, P 1 / c (no. 14), a = 8.9984(2) Å, b 18.0668(6) 10.3178(3) β 95.5070(10)°, V 1669.65(8) Å 3 Z 4, R gt ( F ) 0.0405 wR ref 0.1048, T 150 K.

Язык: Английский

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Crystal structure of 2-bromo-11-(((fluoromethyl)sulfonyl)methyl)-6-methyl-6,11-dihydrodibenzo[c,f][1,2]thiazepine 5,5-dioxide, C₁₆H₁₃BrFNO₄S₂

Zeitschrift für Kristallographie - New Crystal Structures, Год журнала: 2025, Номер unknown

Опубликована: Апрель 23, 2025

Abstract C 16 H 13 BrFNO 4 S 2 , monoclinic, P 1 / c (no. 14), a = 9.1629(2) Å, b 17.9824(4) 10.3488(2) β 95.501(1)°, V 1697.33(6) Å 3 Z 4, R gt ( F ) 0.0331, wR ref 0.0804, T 150 K.

Язык: Английский

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