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1,4-Dihydropyridine Anions as Potent Single-Electron Photoreductants.

ABSTRACT: We report the use of simple 1,4-dihydropyridine anions as a general platform for promoting single-electron photoreductions. In the presence of a mild base, 1,4-dihydropyridines were shown to effectively promote the hydrodechlorination and borylation of aryl chlorides and the photodetosylation of N-tosyl aromatic amines under visible light irradiation. Our studies also demonstrate that the C4 substituent can influence the reactivity of these anions, reducing unwanted side reactions like hydrogen atom transfer and back-electron transfer.

SUBMITTER: Gallage PC

PROVIDER: S-EPMC10928722 | biostudies-literature | 2024 Mar

REPOSITORIES: biostudies-literature

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1,4-Dihydropyridine Anions as Potent Single-Electron Photoreductants.

Gallage Prasadi C PC McKee Mary G MG Pitre Spencer P SP

Organic letters 20240227 9

We report the use of simple 1,4-dihydropyridine anions as a general platform for promoting single-electron photoreductions. In the presence of a mild base, 1,4-dihydropyridines were shown to effectively promote the hydrodechlorination and borylation of aryl chlorides and the photodetosylation of N-tosyl aromatic amines under visible light irradiation. Our studies also demonstrate that the C4 substituent can influence the reactivity of these anions, reducing unwanted side reactions like hydrogen ...[more]

PMID: 38412434

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Intramolecular hydrogen bonds in 1,4-dihydropyridine derivatives.

Project description:1,4-Dihydropyridine (1,4-DHP) derivatives have been synthesized and characterized by 1H, 13C, 15N nuclear magnetic resonance (NMR) spectroscopy, secondary proton/deuterium 13C isotope shifts, variable temperature 1H NMR experiments and quantum-chemical calculation. The intramolecular hydrogen bonds NH⋯O=C and CH⋯O=C in these compounds were established by NMR and quantum-chemical studies The downfield shift of the NH proton, accompanied by the upfield shift of the 15N nuclear magnetic resonance signals, the shift to the higher wavenumbers of the NH stretching vibration in the infrared spectra and the increase of the 1J(15N,1H) values may indicate the shortening of the N-H bond length upon intramolecular NH⋯O=C hydrogen bond formation.

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Comparison between 1,2-Dihydropyridine and 1,4-Dihydropyridine on Hydride-Donating Ability and Activity.

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Novel 1,4-Dihydropyridine Derivatives as Mineralocorticoid Receptor Antagonists.

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Intramolecular C-H···O hydrogen bonding in 1,4-dihydropyridine derivatives.

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First Organocatalytic Asymmetric Synthesis of 1-Benzamido-1,4-Dihydropyridine Derivatives.

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1,1'-[4-(2-Methoxyphenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-diyl]diethanone.

Project description:In the title compound, C(18)H(21)NO(3), the 1,4-dihydro-pyridine ring exhibits a flattened boat conformation. The methoxy-phenyl ring is nearly planar [r.m.s. deviation = 0.0723 (1) Å] and is perpendicular to the base of the boat [dihedral angle = 88.98 (4)°]. Inter-molecular N-H⋯O and C-H⋯O hydrogen bonds exist in the crystal structure.

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Photoredox-Catalyzed Addition of Carbamoyl Radicals to Olefins: A 1,4-Dihydropyridine Approach.

Project description:Functionalization with C1-building blocks are key synthetic methods in organic synthesis. The low reactivity of the most abundant C1 -molecule, carbon dioxide, makes alternative carboxylation reactions with CO2 -surrogates especially important. We report a photoredox-catalyzed protocol for alkene carbamoylations. Readily accessible 4-carboxamido-Hantzsch esters serve as convenient starting materials that generate carbamoyl radicals upon visible light-mediated single-electron transfer. Addition to various alkenes proceeded with high levels of regio- and chemoselectivity.

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The unique reactivity of 5,6-unsubstituted 1,4-dihydropyridine in the Huisgen 1,4-diploar cycloaddition and formal [2 + 2] cycloaddition.

Project description:The three-component reaction of isoquinolines, dialkyl acetylenedicarboxylates, and 5,6-unsubstituted 1,4-dihydropyridines in acetonitrile at room temperature afforded functionalized isoquinolino[1,2-f][1,6]naphthyridines in good yields and with high diastereoselectivity. More importantly, the formal [2 + 2] cycloaddition reaction of dialkyl acetylenedicarboxylates and 5,6-unsubstituted 1,4-dihydropyridines in refluxing acetonitrile gave unique 2-azabicyclo[4.2.0]octa-3,7-dienes as major products and 1,3a,4,6a-tetrahydrocyclopenta[b]pyrroles as minor products via further rearrangement.

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An isoxazole strategy for the synthesis of 4-oxo-1,4-dihydropyridine-3-carboxylates.

Project description:A method has been developed for the preparation of 2-alkyl-6-aryl-, 2-aryl-6-aryl and 2,6-diaryl-5-aryl/hetaryl-substituted methyl 4-oxo-1,4-dihydropyridine-3-carboxylates by Mo(CO)6-mediated ring expansion of methyl 2-(isoxazol-5-yl)-3-oxopropanoates. The high reactivity of 4-oxo-1,4-dihydropyridine-3-carboxylates synthesized provide easy access to 2,4,6-triaryl-substituted and 1,2,5,6-tetrasubstituted nicotinates.

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Direct Enantiomeric Resolution of Seventeen Racemic 1,4-Dihydropyridine-Based Hexahydroquinoline Derivatives by HPLC.

Project description:1,4-Dihydropyridine (DHP) scaffold holds an outstanding position with its versatile pharmacological properties among all heterocyclic compounds. Although most of the commercially available DHPs are marketed as a racemic mixture, the chiral center at C-4 can lead to even opposite pharmacological activities between the enantiomers. In the present study, enantioseparation of seventeen DHP structural analogues, consisting of either pharmacologically active or newly synthesized derivatives, (M2-4, MD5, HM2, HM10, CE5, N11, N10, N7, M11, MC6-8, MC13, MD23, and 42IIP) by high-performance liquid chromatography was investigated using immobilized polysaccharide-based chiral stationary phase, Chiralpak IC column. Due to the solvent versatility of the covalently immobilized chiral stationary phase in enantiomer separation, multiple elution modes including standard normal phase, nonstandard mobile phase, and reversed phase were used to expand the possibility to find the optimum enantioselective conditions for the tested analytes. Under appropriate separation conditions, complete enantiomeric separation was obtained for nearly all compounds except MC6-8 and MC13 which contained two chiral centers. Additionally, the effects of the polar modifier, the additive, and column temperature on the chiral recognition were evaluated. The thermodynamic parameters calculated according to the linear van't Hoff equation indicated that the chiral separations in this study were enthalpy-driven or entropy-driven. Some parameters of method validation such as linearity, limit of quantitation, and repeatability were also measured for all studied compounds to prove the reliability of the method.

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