Catalytic Asymmetric Synthesis of Chiral α,α-Dialkyl Aminonitriles via Reaction of Cyanoketimines

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(18), С. 12329 - 12337

Опубликована: Апрель 25, 2024

Chiral aminonitriles not only are broadly useful building blocks but also increasingly appear as structural motifs in bioactive molecules and pharmaceuticals. The catalytic asymmetric synthesis of chiral aminonitriles, therefore, has been intensively investigated, reflected numerous reports Strecker reactions. Despite such great progress, the α,α-dialkyl a highly selective efficient manner is still formidable challenge. Here, we report new approach for via reaction cyanoketimines with enals. We demonstrate that this could be carried out low 20 ppm catalyst loading.

Язык: Английский

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Strong Bases and beyond: The Prominent Contribution of Neutral Push–Pull Organic Molecules towards Superbases in the Gas Phase

International Journal of Molecular Sciences, Год журнала: 2024, Номер 25(11), С. 5591 - 5591

Опубликована: Май 21, 2024

In this review, the principles of gas-phase proton basicity measurements and theoretical calculations are recalled as a reminder how PA/GB scale, based on Brønsted–Lowry theory, was constructed in (PA—proton affinity and/or GB—gas-phase enthalpy Gibbs energy respectively). The origins exceptionally strong some organic nitrogen bases containing N-sp3 (amines), N-sp2 (imines, amidines, guanidines, polyguanides, phosphazenes), N-sp (nitriles) rationalized. particular, role push–pull development superbasicity region is emphasized. Some reasons for difficulties poly-functional highlighted. Various structural phenomena being relation with acid–base equilibria that should be considered quantum-chemical parameters discussed. preparation methods site protonation briefly reviewed. Finally, recent trends research neutral superbases, leaning toward catalytic other remarkable applications, underlined.

Язык: Английский

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Synthesis of Thioureas from Amines and CS₂ via Photoredox Catalysis

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(1), С. 240 - 240

Опубликована: Янв. 1, 2025

Язык: Английский

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Enantioselective modular synthesis of α-aryl-α-heteroaryl aminonitriles with parts per million organocatalyst loading: mechanistic investigation for stereochemical origins

Organic Chemistry Frontiers, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

An enantioselective Friedel-Crafts reaction of iminonitriles gave chiral α-aryl-α-heteroarylaminonitriles in high yield with good enantioselectivity. Pyrrole and indole additions produced different stereochemistries under the same catalyst, explained by DFT.

Язык: Английский

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Synthesis and Evaluation of the Antiproliferative Activity of the Derivatives of 3,5-Diaryl-3,4-dihydro-2H-pyrrole-2-carboxilic Acids

Molecules, Год журнала: 2025, Номер 30(7), С. 1602 - 1602

Опубликована: Апрель 3, 2025

The metabolic cycle of L-proline plays a crucial role in cancer cell survival, proliferation, and metastasis. A key intermediate the biosynthesis degradation proline is 3,4-dihydro-2H-pyrrole-2-carboxilic acid. direct route for synthesizing substituted derivatives this acid involves cyclization 2-amino-5-oxonitriles. Michael additions [(diphenylmethylene)amino]acetonitrile to enones basic medium—either with aqueous sodium hydroxide or under solid–liquid phase-transfer catalysis conditions using CaO as base—enable synthesis 2-amino-5-oxonitriles single diastereoisomers diastereoisomeric mixtures. Selective removal diphenylmethylene-protecting group, followed by situ acidic conditions, yields trans- cis-3,5-diaryl-3,4-dihydro-2H-pyrrole-2-carbonitriles. reaction nitriles HCl/dioxane/methanol treatment water produces esters amides by-products. In vitro screening synthesized compounds against multiple human lines revealed that some exhibit good high selectivity index. conclusion, synthetic schemes presented offer simple efficient routes preparation acids, exhibiting promising antiproliferative activity.

Язык: Английский

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Nickel(II)-Catalyzed Unexpected [3 + 2] Cycloaddition/[3,3]-Rearrangement of N-Vinyl α,β-Unsaturated Nitrones with 2-Alkynyl Quinazolinones

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 15, 2025

A nickel(II)-catalyzed unexpected [3 + 2] cycloaddition/[3,3]-rearrangement cascade reaction was developed for the preparation of various polysubstituted 1-pyrroline-tethered quinazolinones containing three contiguous stereocenters in moderate to good yields with high diastereoselectivity from N-vinyl cinnamaldehyde nitrones and 2-alkynyl quinazolinones. Polysubstituted pyrrolizine-tethered were obtained when replaced by chalcone nitrones. The present method features a broad substrate scope, [3,3]-rearrangement selectivity diastereoselectivity, two substituent bifurcated types N-heterocycles.

Язык: Английский

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Direct Enantioselective α-C–H Conjugate Addition of Propargylamines to α,β-Unsaturated Ketones via Carbonyl Catalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 11, 2024

Direct asymmetric α-C-H conjugate addition of propargylamines to α,β-unsaturated ketones remains a great challenge due the low α-amino C-H acidity and nucleophilic interference NH

Язык: Английский

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Synthesis of α-Aminonitriles via Ammonium-Catalyzed Reactions of Aminoacetonitrile

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 12, 2024

α-Aminonitriles are not only broadly useful building blocks but also structural motifs in bioactive molecules. The Strecker reaction is one of the most widely used methods for α-aminonitrile synthesis. However, a severe drawback reactions required use stoichiometric amount toxic cyanation reagents. Thus, development greener and applicable method synthesis aminonitriles from readily available starting materials presents an important yet unmet challenge. We developed general new aminoacetonitrile. This utilized off-the-shelf ammonium salts as catalysts, tolerated air moisture, avoided reagents, which rendered it alternative to practiced approach. further illustrated that chiral ammonium-catalyzed asymmetric

Язык: Английский

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New Synthetic Approaches for the Construction of Enantioenriched Molecules Bearing Quaternary Stereocenters

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(21), С. 4294 - 4322

Опубликована: Авг. 17, 2024

Abstract Optically active molecule architectures stand as an important class of organic compounds and occupy a key role in academic industrial communities. Particularly, the molecules bearing quaternary carbon are vital importance because its favorable conformation valuable three‐dimensional molecules, which frequently play broad spectrum functional materials, pharmaceutical relevant natural agrochemicals. Over past few decades, large number synthetic strategies for enantioselective construction with chiral centers have been focus research initiatives. In this review, state‐of‐the‐art toward synthesis enantioenriched stereocenters summarized, could be segmented into four categories: 1) Construction optically by addition to prochiral sp 2 carbon; 2) all‐carbon via substitution at non‐chiral tetra‐substituted 3) kinetic resolution; 4) desymmetrization reactions.

Язык: Английский

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Rel-(2R, 3S)-2-((Diphenylmethylene)amino)-5-Oxo-5-Phenyl-3-(Thiophen-2-Yl)pentanenitrile

Опубликована: Авг. 27, 2024

The reaction of 2-((diphenylmethylene)amino)acetonitrile with (E)-1-phenyl-3-(thiophen-2-yl)prop-2-en-1-one was performed by using 33% NaOH in CH3CN for 30 min at 0°C. main product - rel-(2R,3S)-2-((diphenylmethylene)amino)-5-oxo-5-phenyl-3-(thiophen-2-yl)pentanenitrile isolated and characterized IR, 1H NMR, 13C NMR high-resolution mass spectrometry (HRMS).

Язык: Английский

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