Electrochemical Synthesis of gem‐Difluoro‐ and γ‐Fluoro‐Allyl Boronates and Silanes

Chemistry - A European Journal, Год журнала: 2022, Номер 28(66)

Опубликована: Сен. 6, 2022

Abstract The electrochemical synthesis of fluorinated allyl silanes and boronates was disclosed. addition electrogenerated boryl or silyl radicals onto many α‐trifluoromethyl α‐difluoromethylstyrenes in an undivided cell allowed the formation a large panel synthetically useful gem ‐difluoro γ‐fluoroallyl (64 examples, from 31 % to 95 yield). In addition, scale up reactions under continuous flow showcased using reactor with promising volumetric productivity (688 g.L −1 .h 496 ). Moreover, synthetic utility these building blocks highlighted through versatile transformations. Finally, plausible reaction mechanisms were suggested explain products.

Язык: Английский

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Visible light-promoted defluorinative alkylation/arylation of α-trifluoromethyl alkenes with thianthrenium salts

Green Chemistry, Год журнала: 2024, Номер 26(17), С. 9371 - 9377

Опубликована: Янв. 1, 2024

Defluorinative alkylation and arylation between thianthrenium salts α-trifluoromethyl alkene to afford gem -difluoroolefins by easily recycling thianthrene under visible light irradiation free of metal photocatalyst.

Язык: Английский

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Visible-Light-Induced Three-Component 1,2-Alkylpyridylation of Alkenes via a Halogen-Atom Transfer Process

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(3), С. 1703 - 1708

Опубликована: Янв. 16, 2024

Visible-light-induced three-component 1,2-alkylpyridylation of alkenes with unactivated alkyl iodides and aryl cyanides is reported via a photocatalytic halogen-atom transfer (XAT) strategy. This metal-free protocol utilizes readily available tertiary alkylamine as the terminal reductant to smoothly convert into corresponding carbon radical species. The reaction features broad substrate scope, excellent functional group tolerance, high efficiency, mild conditions. practicability this methodology further demonstrated in late-stage difunctionalization bioactive molecules.

Язык: Английский

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Gem-Difluoroallylation of Aryl Sulfonium Salts

Organic Letters, Год журнала: 2022, Номер 24(48), С. 8753 - 8758

Опубликована: Ноя. 28, 2022

The unprecedented photochemical late-stage defluorinative gem-difluoroallylation of aryl sulfonium salts, which are formed site-selectively by direct C(sp2)─H functionalization, is herein disclosed. This method distinguished its mild reaction conditions, wide scope, and excellent site-selectivity. As showcase examples, a Flurbiprofen Pyriproxyfen derivatives could be late stage gem-difluoroallylated with high yields. Experimental computational investigations were conducted.

Язык: Английский

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Visible-Light Enabled C(sp³)–C(sp²) Cross-Electrophile Coupling via Synergistic Halogen-Atom Transfer (XAT) and Nickel Catalysis

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(8), С. 5442 - 5450

Опубликована: Март 31, 2022

We herein report the first visible-light-mediated cross-coupling of unactivated alkyl iodides with aryl bromides through synergistic halogen atom transfer (XAT) and nickel catalysis. This simple protocol operates under mild reaction conditions tolerates a variety functional groups affording C(sp3)–C(sp2) products in good to moderate yields.

Язык: Английский

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Visible-light-driven selective difluoroalkylation of α-CF₃ alkenes to access CF₂-containing gem-difluoroalkenes and trifluoromethylalkanes

Organic Chemistry Frontiers, Год журнала: 2023, Номер 11(2), С. 458 - 465

Опубликована: Ноя. 23, 2023

A visible-light-mediated selective difluoroalkylation of α-trifluoromethyl alkenes with difluoroalkylating reagents was developed. This protocol allowed the formation gem -difluoroalkene difluoroacetates and trifluoromethylated difluoroacetamides.

Язык: Английский

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Radical-mediated [3 + 2 + 1] annulation of α-polyfluoromethyl alkenes with arylisocyanates enabled by C(sp³)–F activation

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(5), С. 1305 - 1313

Опубликована: Янв. 1, 2024

A conceptually novel single electron transfer strategy for C(sp3)–F activation-enabled [3 + 2 1] annulation of α-polyfluoromethyl alkenes is developed.

Язык: Английский

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Dicarbofunctionalizations of an Unactivated Alkene via Photoredox/Nickel Dual Catalysis

Organic Letters, Год журнала: 2022, Номер 24(34), С. 6261 - 6265

Опубликована: Авг. 19, 2022

1,2-Dicarbofunctionalization of unactivated olefin has been reported under photoredox/nickel dual catalysis. The mildness the visible-light-mediated reaction allows use various alkyl and aryl electrophiles with several sensitive functional groups. protocol was equally applied for late-stage diversification drugs biologically active molecules. Investigations elucidated importance catalysis α-amino-radical-mediated halogen atom transfer provided us nickel complexes involved in reaction.

Язык: Английский

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Oxalates as Activating Groups for Tertiary Alcohols in Photoredox-Catalyzed gem-Difluoroallylation To Construct All-Carbon Quaternary Centers

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(12), С. 8237 - 8247

Опубликована: Май 25, 2022

Construction of challenging and important all-carbon quaternary centers has received growing attention. Herein, with oxalates as activating groups for tertiary alcohols, we report photoredox-catalyzed gem-difluoroallylation to construct enabled by efficient radical addition α-trifluoromethyl alkenes. This transformation shows good functional group tolerance both alkenes oxalates. Moreover, this strategy is also successfully applied the synthesis monofluoralkenes from corresponding electron-rich gem-difluoroalkenes cesium alkyl under modified conditions.

Язык: Английский

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Photo-Induced Formal Trifluoropropanation of Organic Halides

ACS Catalysis, Год журнала: 2023, Номер 13(13), С. 8624 - 8630

Опубликована: Июнь 14, 2023

CF3-containing molecules are frequently encountered in many best-selling pharmaceutical drugs. Consequently, a large number of methods have been developed for introducing CF3 group into organic compounds. However, innovative protocols enabling direct access to alkyl-CF3 moieties still sought after. In this context, we report visible-light-induced formal trifluoropropanation various alkyl and aryl halide derivatives using the 2-Bromo-3,3,3-trifluoro-1-propene (BTP) as readily available building block. Our strategy relies on use catalytic system merging amount supersilane NaBH4 an additional reductant. These mild reaction conditions compatible with range functional groups. Finally, double deuterium incorporation was obtained upon replacement NaBD4 under these conditions, leading formation hitherto unknown α,α-d2-CF3

Язык: Английский

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