Regioselective synthesis of 3,3-bis(indolyl)propanoic acid derivatives by iron(III)-catalyzed hydroarylation of propynoic acid derivatives with indoles

Intermolecular hydroarylation of propynoic acid and its esters with indoles proceeded efficiently in acetic acid under a catalytic system of FeCl₃/3AgOTf and afforded the corresponding 3,3-bis(indol-3yl)propanoic acids and their esters in high yields. In the case of 2-methylindole, 3-indolylacrylic acid and its ethyl ester were obtained in high yields. This iron-catalyzed hydroarylation showed a high regioselectivity at the 3-position of indoles and a high utility for the synthesis of bis(indol-3-yl) compounds, which are important for biological and pharmaceutical fields.     

Synthesis of poly-3,3-bis(chloromethyl)-oxacyclobutane (penton) derivatives

The derivatives of poly-3,3-bis(chloromethyl)oxacyclobutane were prepared by the reaction of the chloromethyl group with organic alkali salts at 100–130°C. in dimethyl sulfoxide. Various reagents were used, including sodium cyanide, sodium acetate, sodium thiophenolate, sodium phenolate, sodium methoxide, sodium diethyl malonate, and potassium phthalimide. For all the substitution reactions, the infrared spectra and elementary analyses substantiated the structures of the designated products. The intrinsic viscosities of the derivatives decreased with increasing the reaction time. It was found that the ions of these salts are strong nucleophiles in dimethyl sulfoxide.     

Synthesis, resolution and applications of 3,3′-bis(RO)-MeO-BIPHEP derivatives

A series of optically pure 3,3′-bis(RO)-MeO-BIPHEP derivatives are prepared and used in palladium catalyzed asymmetric transformations. The phosphine oxide of (±)-5 is prepared in four steps from p-methoxyphenol and resolved using the novel resolving reagent chloro(l-menthoxy)dimethylsilane. Subsequent conversions provide catalysts 8 and 9. Ligands 6, 7 and 10 are prepared in six steps from p-methoxyphenol and the phosphine oxides of 6 and 7, and 10 are resolved using di-p-toluoyl- and dibenzoyl-l-tartaric acid, respectively. (R)-3,3′-Bispivalate 8 is superior to the other catalysts in asymmetric Heck reaction with 2,3-dihydrofuran while (R)-(+)-bis(tolyloxy) 10 and (+)-(R)-sugar derivative 9 are better in the Pd-catalyzed polyene cyclization; however, the absolute sense of chirality in the product from the polyene cyclization was reversed to that obtained when (R)-(+)-BINAP and (R)-(+)-MeO-BIPHEP were used.     

Strukturuntersuchungen an Poly-3,3-bis(chloromethyl)-oxacyclobutan

Zusammenfassung Im Elektronenbeugungsbild zeigen aus der Schmelze gewachsene Penton-Sphärolithe eine bevorzugte Orientierung der Elementarzelle: diea-Achse liegt radial und dieb- undc-Achse tangential.Penton kristallisiert aus einer Xylollösung in derForm. Die aus dem Elektronenbeugungsbild bestimmte Elementarzelle konnte mit Röntgenweitwinkelaufnahmen an orientiertem Material bestätigt werden:=17,85 Å, b=8,16 Å, c=4,8 Å. Röntgenkleinwinkeluntersuchungen zeigen bei Kristallisationstemperaturen zwischen 60 und 135 °C eine Zunahme der Langperiode von 70 auf 135 Å. Elektronenmikroskopisch gemessene Lamellendicken stimmen mit den Langperioden überein.

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Summary Penton-spherulites grown from the melt show a favoured orientation in the electron-diffraction-pattern thea-axis being radial and theb- andc-axis tangential.Penton crystallizes from a xylene-solution in the-form. The elementary-cell, determined from the electron-diffraction-pattern, was confirmed byX-raywide-angle-patterns of oriented material:=17,85 Å,b=8,16 Å,c=4,8 Å.X-ray-low-angle-analysis shows an increase of the long-period from 70 to 135 Å at crystallisation-temperatures from 60 to 135 °C, respectively. The thicknesses of the lamellas, as measured in the electronmicroscope, are in convenience with the long-periods.

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Herrn Professor Dr.K. -H. Hellwege und Herrn Dr.U. Johnsen danken wir für Anregung und Diskussionen.     

Hedrit-Strukturen des Poly-3,3-bis(chloromethyl)-oxirans

Zusammenfassung Bei der Kristallisation des Poly-3,3-bis(chloromethyl)-oxirans entstehen quadratische Strukturen, die wir in Analogie zu Kristallstrukturen des Polyoxymethylens als Hedrite bezeichnen. In der Mitte der Hedrite befindet sich eine als Krater ausgebildete Schraubenversetzung, um die sich die Lamellenkristalle herumlagern. Die Hedrite bilden eine morphologische Zwischenform zwischen Einkristallen und Sphärolithen.

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Summary Poly-3,3-bis(chloromethyl)oxacyclobutane crystallizes in the form of square structures, which we called hedrites analogous to the morphological structures of polyoxymethylene. In the centre of the hedrites there is a screw dislocation in the form of a crater, which is surrounded by the lamellas. The hedrites are a morphological structure between single crystals and spherulites.

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Herrn Professor Dr.K.- H. Hellwege danke ich für die Anregung zu dieser Arbeit und für fördernde Diskussionen.     

Diaziridine-3,3-dicarboxylic acid derivatives

Conclusions The first functional diaziridines, and specifically the diaziridine-3,3-dicarboxylic acid derivatives, were synthesized, which are suitable for separating into the enantiomers by inserting the moiety of an optically active alcohol and separation of the diastereomers, with subsequent removal of the asymmetric substituent by aminolysis, the possibility of which was shown.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2823–2827, December, 1974.     

2-Aziridino- and 2-diaziridino-3,3-bis(trifluoromethyl)aziridines

3,3-Bis(trifluoromethyl)-1-azirine, formed by the reaction of 1-arenesulfonyloxy-2,2-bis(trifluoromethyl)aziridines with nucleophilic reagents, reacts with aliphatic amines with ring-opening and formation of formamidines. With aziridines and diaziridines having a lower electron-donor capability of the nitrogen atom, it forms the adducts -2-aziridino- and -2-diaziridino-3,3-bis(trifluoromethyl)aziridines. All the isomers theoretically possible were recorded for these derivitives by the dynamic NMR method.Article 58 of the series Asymmetric nitrogen. For Article 57, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 472–479, April, 1988.     

Morphologische Strukturen des Poly-3,3-bis(chloromethyl)-oxirans

Zusammenfassung Poly-3,3-bis(chloromethyl)-oxiran kristallisiert aus der Schmelze in Form von Sph?rolithen mit „blumenblattartiger“ Struktur. Das für Sph?rolithe typische Ausl?schungskreuz ist nicht immer klar ausgebildet. Aus einer übers?ttigten Xyloll?sung kristallisiert die Substanz als rautenf?rmige Einkristalle. Mit der Annahme, da\ die Molekelketten wie beim Poly?thylen senkrecht zur Rautengrundfl?che stehen und regelm?\ig gefaltet sind, folgt aus dem Elektronenbeugungsbild dieser Einkristalle eine orthorhombische Elementarzelle mit den folgenden Abmessungen:a=17,85 ?,b=8,16 ? (c=4,8 ?, aus der Literatur bekannt).

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Summary Poly-3,3-bis(chloromethyl)oxacyclobutane crystallizes from the melt as “petal-shaped” spherulites. The extinction cross, typical for spherulites, is not well developed in all cases. From a solution of xylene the substance crystallizes in the form of flat lozenges. We assume, that the molecules are perpendicular to the plane of the crystals and that they are regularly folded as in the case of polyethylene. Therewith and from the electron diffraction pattern we found the unit cell to be orthorhombic with the dimensions:a=17,85 ?,b=8,16 ? (c=4,8 ?, from literature).

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Herrn Prof. Dr.K.-H. Hellwege und Herrn Dr. W.Knappe danke ich für die Anregung zu dieser Arbeit, Herrn Dr.U. Johnsen für viele f?rdernde Diskussionen, sowie Herrn Dipl.-Phys.D. Kockott für die Ausführung derDebye-Scherrer-Aufnahmen.     

Synthesis of 2,5-diethyl-3,4-bis(trifluoromethyl)furan and its derivatives

The addition reaction of propionaldehyde to hexafluoro-2-butyne ( 1 ) under γ-ray irradiation gave trans-6,6,6-trifluoro-4-trifluoromethyl-4-hexen-3-one ( 2 ) and 4,5-bis(trifluoromethyl)octa-3,6-dione ( 3 ). The latter compound was treated with sulfuric acid to give 2,5-diethyl-3,4-bis(trifluoromethyl)furan ( 4a ). Several reactions, such as bromination, dehydrobromination and oxidation, were carried out to prepare derivatives of 4a .     

An access to original 3,3-bis(phospholyl)lactones

The reaction of lithium 3,4-dimethylphospholide with dicarboxylic acid dichlorides yields the original 3,3-bis(3,4-dimethylphospholyl)lactones via an unexpected cyclization reaction. One of the products has been characterized by X-ray crystal structure analysis of its bis(pentacarbonylmolybdenum) complex.     

2-Alkylisoxazolidine-3,3-dicarboxylic acid derivatives

1,3-Dipolar cycloaddition of,-bis(alkoxycarbonyl)-N-alkylnitrones to olefins gave 2-alkylisoxazolidine-3,3-dicarboxylic acid esters, the yields of which are determined by the steric conditions and are virtually independent of the electronic effect of the substituents attached to the C=C bond of the dipolarophiles. The structures of the compounds obtained were established by analysis of the PMR spectra. The retention of the cis configuration of the substituents in the isoxazolidines obtained from maleic acid esters constitutes evidence for a one-step, four-center, concerted cycloaddition mechanism. The energy parameters for inversion of the nitrogen atom of dimethyl 2,5,5-trimethylisoxazolidine-5,5-dicarboxylate were measured.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 599–603, May, 1979.     

(2,2,2-Trinitroethoxy)acetic acid and its derivatives

The influence of the trinitromethane salt cations and the substituents in the alkyl moiety of chloromethyl ethers of alcohols on the yields of trinitroethyl ethers of the substituted alcohols formed from them was established. On this basis a representative series of previously unavailable trinitroethanol ethers was synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2540–2544, November, 1991.     

Difluoro(pentafluorothio)acetic acid and its derivatives

Russian Chemical Bulletin -