Nickel-Catalyzed Modular Four-Component 1,4-Alkylcarbonylation of 1,3-Enynes to Tetra-Substituted CF₃–Allenyl Ketones

ACS Catalysis, Год журнала: 2024, Номер 14(4), С. 2144 - 2150

Опубликована: Янв. 25, 2024

The modular four-component carbonylation of unsaturated hydrocarbons represents an elegant strategy for the one-pot synthesis complex carbonyl compounds. However, this is currently focused on 1,2-difunctionalization olefins or alkynes, and 1,4-alkylcarbonylation 1,3-enynes remains unexplored. In study, we report a Ni-catalyzed CF3-containing under 1 atm CO, which affords tetra-substituted CF3-allenyl ketones with good yields selectivity. This protocol features mild conditions, broad substrate scope, acceptable functional group compatibility. Control experiments revealed that reactivity oxime esters (regulated by leaving groups) polarity matching are crucial success cascade. Preliminary mechanistic studies suggest acyl nickel key intermediate in transformation.

Язык: Английский

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Three-Component Synthesis of Multiple Functionalized Allenes via Copper/Photoredox Dual Catalyzed 1,4-Alkylcyanation of 1,3-Enynes

Organic Letters, Год журнала: 2024, Номер 26(9), С. 1834 - 1839

Опубликована: Фев. 22, 2024

Efficient access to multiple functionalized allenes via a three component 1,4-alkylcyanation of enynes with cyclic alcohol derivatives in the presence trimethylsilyl cyanide (TMSCN) under copper/photoredox dual catalysis has been developed. Both easily transformable aldehyde and cyano groups were introduced tetra-substituted through light-induced C–C bond cleavage butanol pentanol derivatives. The reactions proceeded smoothly mild conditions broad functional tolerance.

Язык: Английский

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Copper-catalyzed photoredox 1,4-amidocyanation of 1,3-enynes with N-amidopyridin-1-ium salts and TMSCN: Facile access to α-amido allenyl nitriles

Chinese Chemical Letters, Год журнала: 2024, Номер 35(11), С. 109685 - 109685

Опубликована: Март 1, 2024

Язык: Английский

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Copper/Photoredox‐Catalyzed Regioselective 1,4‐Addition to 1,3‐Enynes: A Convenient Access to Perfluoroalkylated Allenes

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(17), С. 2023 - 2028

Опубликована: Апрель 30, 2024

Comprehensive Summary A general and broadly applicable copper photoredox dual‐catalyzed multicomponent 1,4‐perfluoroalkylcyanation of 1,3‐enynes has been developed. This protocol enjoys success with high regioselectivity, mild reaction conditions, excellent functional‐group tolerance, allowing the facile synthesis structurally diverse perfluoroalkylated allenes from readily available fluoroalkyl halides, TMSCN in a one‐pot manner. reasonable mechanism proposed according to series control experiments.

Язык: Английский

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Electrochemically mediated synthesis of trifluoromethylallenes

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(12), С. 3485 - 3490

Опубликована: Янв. 1, 2024

Herein, we report electrochemically mediated trifluoromethylallene synthesis via the rearrangement of trifluoromethyl-containing 1,3-enynes under action silicon or boron radicals, with good selectivity and without external oxidants.

Язык: Английский

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Photoredox-Catalyzed Sequential Decarboxylative/Defluorinative Aminoalkylation of CF₃-Alkenes with N-Arylglycines

Organic Letters, Год журнала: 2024, Номер 26(28), С. 6030 - 6034

Опубликована: Июль 8, 2024

A photoredox-catalyzed sequential decarboxylative/defluorinative aminoalkylation of CF3-alkenes with N-arylglycines is described. This metal-free and redox-neutral protocol provided efficient access to the monofluoroalkenyl-1,5-diamines in good yields excellent functional group compatibility. Mechanistic studies revealed that reaction proceeds via a radical pathway gem-difluoroalkenyl amine as an intermediate.

Язык: Английский

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Trifluoromethyl Group (CF₃) Induced Regioselective Larock Indole Synthesis from Unsymmetric β-CF₃-1,3-enynes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 24, 2025

The indole skeleton exists widely in natural products, pharmaceuticals, and materials. We disclose here a trifluoromethyl group induced regioselective Larock synthetic method from unsymmetric 2-CF3-1,3-enynes. presence of is determinable for the regioselectivity. Once CF3 was replaced with methyl or phenyl group, ratio 1:1 to 1:1.4 isomers were obtained. This strategy features good regioselectivity, broad substrate scope, high functional tolerance. protocol reported offers an alternative solution rare 3,4-functionalization products further transformed show distinctive reactivity hydroboration–oxidation hydro-bromination.

Язык: Английский

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Nickel-catalyzed regiodivergent sulfonylarylation of 1,3-enynes to access allenes and dienes

Chemical Science, Год журнала: 2024, Номер 15(33), С. 13271 - 13278

Опубликована: Янв. 1, 2024

The radical-mediated difunctionalization of 1,3-enynes facilitates rapid access to structurally diverse allenes and dienes.

Язык: Английский

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Diastereoselective 1,2-difunctionalization of 1,3-enynes enabled by merging photoexcited Hantzsch ester with chromium catalysis

Organic Chemistry Frontiers, Год журнала: 2023, Номер 11(2), С. 284 - 289

Опубликована: Окт. 20, 2023

We present a comprehensive account of the regio- and diastereoselective radical multicomponent 1,2-dialkylation 1,3-enynes via photoexcited Hantzsch ester chromium co-catalysis to furnish highly valuable homopropargylic alcohols.

Язык: Английский

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Electrochemically Enabled Hydroxyphosphorylation of 1,3-Enynes to Access Phosphinyl-Substituted Propargyl Alcohols

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(15), С. 10796 - 10804

Опубликована: Июль 19, 2024

Catalytic difunctionalization with the direct activation of (O)P-H bonds has been recently established as a potentially robust platform to generate valuable organophosphorus compounds. In terms 1,3-enynes, despite various catalytic methods developed for hydrophosphorylation, radical-mediated hetero-functionalization two different atoms less explored. this study, we disclosed an electrochemically induced hydroxyphosphorylation 1,3-enynes construction phosphinyl-substituted propargyl alcohols. The system involves both arylphosphine oxides and oxygen in ambient air no external metal or additive needed. use electrochemistry ensures regioselective, atom-economic eco-friendly process. This strategy highlights advantages mild reaction conditions, readily available starting materials broad substrate scope, showing its practical synthetic value organic synthesis.

Язык: Английский

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