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Solvent-free synthesis of 1-(hydroxyquinolyl)- and 1-(hydroxyisoquinolyl)- 1,2,3,4-tetrahydroisoquinolines by modified mannich reaction

The solvent-free synthesis of 1-(hydroxyquinolyl)- and 1- (hydroxyisoquinolyl)-1,2,3,4-tetrahydroisoquinoline derivatives is reported. The tested reaction conditions involved classical heating at 80-100 C and microwave agitation at the same temperature. Both reaction conditions yielded the compounds in good yield (57-92%), but the use of microwave conditions allowed the reaction time to be decreased. Georg Thieme Verlag Stuttgart New York.

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Reference:
Isoquinoline – Wikipedia,
Isoquinoline | C9H2424N – PubChem

 

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Novel Photochemical-Diradical Cyclization Methods for Protoberberine Alkaloid Synthesis. Preparation of (+/-)-Xylopinine and (+/-)-Stylopine

A new synthetic approach to members of the protoberberine alkaloid family based upon a photochemical-diradical cyclization methodology is described.

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HALO DERIVATIVES OF 8-AZA-D-HOMOGONANES

A simple one-stage method was developed for synthesizing 15,17-dihalo and 17-halo derivatives of 16,16-dimethyl-8-aza-D-homogona-1,3,5(10),13-tetraene-12,17a-diones.The reaction proceeds regio- and stereoselectively, yielding 17-halo derivatives of 8-aza-D-homogonanes from 4-halo-2-acetyldimedones and 15,17-dichloro derivative from 4,6-dichloro-2-acetyldimedone.The 17-halo derivatives exist in solutions as a mixture of cis and trans isomers at C17 with respect to C9H as a result of keto-enol equilibrium at C17a.In the crystalline state only the trans isomer occurs.In the presence of acids an enolimmonium derivatives with trans arrangement of the halogen at C17 and C9H is formed, which exists only in solution.We isolated, together with the 15,17-dihalo derivative, a mino product, which was assigned the structure of cyclopropano<2',3':15,16>-8-azogonane on the basis of physicochemical data.

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Difluorinated Danishefsky’s Diene: A versatile C4 building block for the fluorinated six-membered rings

(equation presented) A Mg(0)/Me3SiCl system was found to be affective for the preparation of difluoro Danishefsky’s dienes 2, which involves selective C-F bond cleavage of trifluoromethyl ketones 3. Subsequent hetero Diels-Alder reactions of 2 with aldehydes and imines gave a variety of fluorinated six-membered heterocycles.

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Synthesis of 1-(2-oxoalkyl)-2-acyltetrahydro- isoquinolines by alpha-amidoalkylatlon of methylene active carbonyl compounds with n-acyliminium intermediates

Intermolecular alpha-amidoalkylation reaction of methylene active carbonyl compounds with N-acyliminium salts of 3,4-dihydroisoquinolines and acyl chlorides has been used for synthesis of 1-(2-oxoalkyl)- 2-acyltetrahydroisoquinolines.

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Isoquinoline – Wikipedia,
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Asymmetric Synthesis of Isoquinoline Alkaloids: 2004-2015

In the past decade, the asymmetric synthesis of chiral nonracemic isoquinoline alkaloids, a family of natural products showing a wide range of structural diversity and biological and pharmaceutical activity, has been based either on continuation or improvement of known traditional methods or on new, recently developed, strategies. Both diastereoselective and enantioselective catalytic methods have been applied. This review describes the stereochemically modified traditional syntheses (the Pictet-Spengler, the Bischler-Napieralski, and the Pomeranz-Fritsch-Bobbitt) along with strategies based on closing of the nitrogen-containing ring B of the isoquinoline core by the formation of bonds between C1-N2, N2-C3, C1-N2/N2-C3, and C1-N2/C4-C4a atoms. Methods involving introduction of substituents at the C1 carbon of isoquinoline core along with syntheses applying various biocatalytic techniques have also been reviewed.

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Synthesis of (-)-(S)-norlaudanosine, (+)-(R)-O,O-dimethylcoclaurine, and (+)-(R)-salsolidine by alkylation of an alpha-aminonitrile

A short asymmetric synthesis of 1-substituted 1,2,3,4- tetrahydroisoquinoline alkaloids by deprotonation of an unprotected alpha-aminonitrile and alkylation of the resulting carbanion followed by spontaneous elimination of HCN and asymmetric reduction is described. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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The Absolute Best Science Experiment for 6,7-Dimethoxy-3,4-dihydroisoquinoline

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ELECTRON SPECTRA OF 1-TETRALONE, HOMOPHTHALIDE, 3,4-DIHYDROISOQUINOLINE, AND 3,4-DIHYDROISOQUINOLINIUM COMPOUNDS

The electron spectra of 1-indanone (I), 1-tetralone (II), phthalide (III), homophthalide (IV) 3,4-dihydroisoquinoline (VII), and 3,4-dihydroisoquinolinium (VIII) compounds, substituted by electron donating groups (hydroxy, methoxy or methylendioxy groups) on the aromatic nucleus, resemble when the electron donors are at the same distance from the electron accepting substituent.In the compounds VII and VIII, the electron spectra were measured in ethanol at acidic and alkaline pH, and the change in the spectra of the compounds VIII in alkaline medium was clarified.

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A free radical chain mechanism is proposed for the Knabe reaction and the accompanying elimination reaction on account of their nonintegral reaction order and of successful inhibition experiments. 3,4-Dimethoxybenzyl radicals are the chain carrying species.Battersby’s synthesis of N-methylpavine (19) from 1,2-dihydro-2-methylpapaverine (9) is dependent on the presence of formic acid as radical chain inhibitor.In the presence of inhibitors 1-benzyl-1,4-dihydro-2-methylisoquinolinium ions like 10 are persistent species whose chemistry can now be investigated.

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Treatment of cyclic imines with 3,3?-disubstituted binaphthol modified allylboronates provides the expected allylated products in good yields and with high stereoselectivities (91-99% ee). The products may be readily transformed into various alkaloids. Copyright

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