Research Progress on Transition Metal Catalyzed Hydrocarbonation Reactions of N-Allenamines

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(1), P. 151 - 151

Published: Jan. 1, 2025

Language: Английский

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Construction of C–N and C–O bonds based on N-allenamide functionalization

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(46), P. 9069 - 9084

Published: Jan. 1, 2022

The review covers recent advances in the development of new methods involving amination and alkoxylation reactions on N -allenamides covering cycloaddition, carbofunctionalization, halogenofunctionalization as well hydrofunctionalization reactions.

Language: Английский

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Efficient synthesis of β-substituted amines via combining deoxygenation of amides with photochemical organocatalysis

Cell Reports Physical Science, Journal Year: 2022, Volume and Issue: 3(7), P. 100955 - 100955

Published: June 20, 2022

Catalytic deoxygenative conversion of amides to substituted amines is an efficient pathway for amine synthesis. α-Substituted are generally obtained by classic nucleophilic addition nucleophiles active electrophilic intermediates formed from amides. Here, we develop a reaction that combines iridium catalysis and photochemical organocatalysis, giving structurally diverse β-substituted tertiary alkylamines with moderate excellent yields (up 93%) broad substrate scope (57 examples). Mechanistic studies suggest the combination (Ir)-catalyzed partial reduction organocatalysis α-bromoketones under visible light plays crucial role in cross-coupling these two readily accessible feedstocks. The radicals act as functionalization partners in-situ-formed enamine Ir-catalyzed instead traditional iminium ions, leading formation amines.

Language: Английский

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Towards a More Sustainable Photocatalyzed α‐Arylation of Amines: Green Solvents, Catalyst Recycling and Low Loading

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(2), P. 252 - 262

Published: Jan. 7, 2023

Abstract A more sustainable and efficient protocol for the photocatalytic α‐amino arylation promoted by fac ‐Ir(ppy) 3 was developed. Three noteworthy results were achieved: i) replacement of toxic medium DMA with greener solvents NBP NHP, concurrent improvement process efficiency lowering both amine base amount; ii) development a recycling solvent NHP commercially available costly photocatalyst , achieving environmental economic benefits. This approach to recovery avoids very demanding catalyst structural modifications; iii) in green proved be scalable up 10 mmol limiting reagent, maintaining excellent performance also loading down 0.05 mol%. is first example α‐arylation amines such low amount catalyst. Lastly, versatility this demonstrated extending use another photoredox process. magnified image

Language: Английский

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Selective Hydrofunctionalization of N-Allenyl Derivatives with Heteronucleophiles Catalyzed by Brønsted Acids

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(4), P. 2320 - 2342

Published: Feb. 1, 2024

In this study, we present a novel and environmentally sustainable protocol for the γ-hydrofunctionalization of N-allenyl compounds using various heteronucleophiles catalyzed solely by simple Brønsted acids. The method displays remarkable attributes, highlighting its sustainability, efficiency, regio- stereoselectivity, as well versatile applicability to diverse heteroatom-containing enamides. Notably, our approach eliminates need metal catalysts toxic solvents, representing significant advancement in greener chemistry practices. We demonstrate broad scope successfully scaling up reactions gram-scale syntheses, underscoring robustness potential industrial implementation. resulting γ-heterosubstituted enamides offer new possibilities further synthetic transformations, yielding highly functionalized with applications. Mechanistic investigations reveal pivotal role CSA catalyst, enabling alcohol addition via covalent activation mode.

Language: Английский

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Synthesis of 2-Aminofurans and 2-Aminothiophenes through Elemental Sulfur-Promoted Switchable Redox Condensation Reaction of Enaminones with Methylene Nitriles

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(22), P. 15312 - 15326

Published: Nov. 7, 2022

Herein, we report an elemental sulfur-promoted switchable redox condensation reaction that can selectively prepare 2-aminofurans and 2-aminothiophenes from the corresponding enaminones methylene nitriles, respectively. Mechanistic studies demonstrated enaminones, as dual nucleophiles, reacted with nitrile acetate to produce via 3,5-annulation under promotion by sulfur. These reactions used readily available starting materials, transition metal-free, eco-friendly procedures, gram-scale syntheses, wide functional group tolerance. The methodology may be useful for construction of 2-aminofuran 2-aminothiophene derivatives potential biological activity.

Language: Английский

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PhI(OAc)₂-Mediated Regioselective Hydrothiolation of Allenamides with Thiophenol via a Radical Process: Synthesis of Vinyl Sulfides

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(22), P. 15626 - 15638

Published: Oct. 27, 2023

An efficient PhI(OAc)2-mediated regioselective hydrothiolation of allenamides with thiophenol via a radical process was developed to create workable route vinyl sulfides. The reaction exhibits good functional group tolerance and high efficiency, affording the products in excellent yields. Mechanistic investigations indicated that cascade proceeds through an allyl intermediate, which is formed addition PhS central carbon allenamides. Moreover, also selenophenol, providing corresponding product, selenide, 99% yield.

Language: Английский

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Recent Progress in Free Radical Transformations of Allenamides

Current Organic Synthesis, Journal Year: 2024, Volume and Issue: 21(7), P. 889 - 902

Published: Jan. 4, 2024

Abstract: Allenamides are special allenes, and the unique reactivity, selectivity (both stereoselective regionally selective) stability of allenamides have been widely studied. In this review, development free radical transformation over last few years will be summarized. This review discusses in detail three parts: intermolecular addition to C- X (X = N, S, O, Se) bonds, metal salt mediated cyclization allenamides, photocatalytic allenamides. addition, reasonable details mechanisms provided for vast majority these transformations.

Language: Английский

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Synthesis of Difuropyridines from Chitin‐Derived 3‐Acetamidofuran and their Application to Photocatalytic Reactions

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 18, 2024

Abstract Difuropyridines have been prepared from aldehydes and chitin‐derived 3‐acetamidofuran (3AF) under acid‐catalyzed conditions. were comprehensively synthesized for the first time. The difuropyridines can be applied to prepare fluorescent probe analogs or catalyze decarboxylative reactions as photocatalysts.

Language: Английский

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Synthesis of Alkyl Sulfones via a Photocatalytic Multicomponent Reaction of Aryldiazo Tetrafluoroborate Salts, Styrene Derivatives, and Sodium Metabisulfite

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 25, 2024

Practical visible-light-induced synthesis of alkyl sulfones has been achieved via a multicomponent reaction aryldiazo tetrafluoroborate salts, styrene derivatives, thiophenol and sodium metabisulfite in the presence rhodamine B.

Language: Английский

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