Palladium-catalyzed electrophilic substitution of allyl chlorides and acetates via bis-allylpalladium intermediates

Palladium-catalyzed electrophilic allylic substitution of functionalized allyl chlorides and allyl acetates can be achieved in the presence of hexamethylditin under mild and neutral reaction conditions. This efficient one-pot procedure involves palladium-catalyzed formation of transient allylstannanes followed by generation of a bis-allylpalladium intermediate, which subsequently reacts with electrophiles. Using this catalytic transformation, various aldehydes and imines can be allylated providing highly functionalized homoallyl alcohols and amines. Furthermore, tandem bis-allylation reactions could be performed by employing tosyl isocyanate and benzylidenemalonitrile as substrates. A particularly interesting mechanistic feature of this reaction is that palladium catalyzes up to three different transformations in each catalytic cycle. Various allylic functionalities, including COOEt, CONH(2), COCH(3), CN, Ph, and CH(3), are tolerated in the catalytic reactions due to the application of neutral and mild reaction conditions. The substitution reaction occurs with very high regioselectivity at the branched allylic terminus. Moreover, in several reactions, a high stereoselectivity was observed indicating that this new catalytic process has a high potential for stereoselective synthesis. The regioselectivity of the reaction can be explained on the basis of DFT calculations. These studies indicate that the allylic substituent prefers the gamma-position of the eta(1)-allyl moiety of the reaction intermediate.     

A chemoenzymatic total synthesis of ent-bengamide E

The cis-1,2-dihydrocatechol 3, which can be obtained in enantiomerically pure form by microbial dihydroxylation of bromobenzene, has been converted into the enantiomer, ent-1, of the cyclolysine-based marine natural product bengamide E (1).     

Can the highest occupied molecular orbital of the uranyl ion be essentially 5f?

Recent relativistic calculations on the uranyl ion suggest that the low wave numbers of the first electron transfer bands are due to a bonding 5f-like orbital containing the two loosest bound electrons. Comparison with UF₆ makes it more likely that if indeed σ_u (and not π_u) is the highest occupied MO, it is rather due to “pushing from below” by U 6p (like N 2s in N₂).     

Modified Potentiometric Sensors for the Separate Determination of Cationic Surfactants

The main electrochemical and performance characteristics of solid-contact sensors for cationic surfactants based on an organic cetylpyridinium–tetraphenylborate ion exchanger were determined. It was found that the surface of the sensors for cationic surfactants can be modified with poly(vinyl chloride) molecular sieves. The modified electrodes can separately determine alkylpyridinium homologues with different lengths of hydrocarbon radicals (C₁₀–C₁₈).     

Zur Existenz von zwei Kristallmodifikationen der Mellitsäure

Zusammenfassung Es wurde röntgenorgraphisch und mit Hilfe derDTA, festgestellt, daß die Mellitsäure nur in einer Modifikation, der orthorhombischen¹, vorliegt. Die Darstellung der Mellitsäure^2,3 wurde in Einzelheiten modifiziert. Die Reinheit der Präparate wurde spektroskopisch, im IR- bzw. UV-Gebiet, und mit Hilfe der Papierchromatographie geprüft.

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by means of X-ray analysis and DTA it was found that mellitic acid exists only in the orthorhombic modification. The preparation of mellitic acid was modified in part. The purity ot the samples obtained was checked by IR-and UV-spectroscopy and by paper chromatography.

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Zur Kenntnis von Salzen einiger aromatischer Polycarbonsäuren, 3. Mitt.; 2. Mitt.:B. Hájek, E. Kálalová undF. Petr, Z. Chem.5, 230 (1965).

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Gewidmet dem Andenken an Professor Dr.Hans Meyer meinen Lehrer an der ehemaligen Deutschen Universität in Prag. Prof.Meyer geboren am 31. März 1871 in Wien, gestorben am 28. November 1942 in Theresienstadt, beschäftigte sich eingehend (mitH. Raudnitz u. a.) mit der Darstellung und Untersuchung der Mellitsäure und ihrer Derivate.     

Zur Automatisierung der Auswertung bei der quantitativen Spektralanalyse

Zusammenfassung Die Eigenschaften der photoelektrischen und photographischen Registrierung von Spektren werden besprochen und die Bedeutung der photographischen Registrierung für die Verfahrensentwicklung und Routineanalyse von Proben wechselnder Zusammensetzung hervorgehoben. Das Programmsystem für den elektronischen Digitalrechner und verschiedene Möglichkeiten der Datenerfassung werden beschrieben. Durch diese Automatisierung der Auswertung wird gegenüber dem herkömmlichen Rechenbrettverfahren eine Beschleunigung um den Faktor 200 erreicht.

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Summary The characteristics of the photoelectric and photographic registration of spectra are discussed and the importance of the photographic registration for the development of methods and the routine analysis of samples of changing composition is emphasized. The program system for the electronic digitalcomputer and different possibilities of data collecting are described. Automating the evaluation has resulted in a speeding-up factor of 200 compared with the traditional computing board method.

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Die obige Arbeit wurde erwähnt von Herrn Dr. Pohl am 6. 10. 1964 in Düsseldorf in seinem Vortrag Erfassen und Verwerten von chemischen Daten. [Diese Z. 209, 19 (1965).]

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Außerdem wurde uns die Arbeit von Tunnicliff und Weaver, Analytical Chemistry 36, 2318 (1964), erst nach Abschluß unserer Arbeit bekannt. Die Autoren befassen sich mit einer ähnlichen Aufgabe, wobei allerdings das Problem der Linienauswahl eingehender behandelt wird als bei uns.     

Helical water chains in aquapores of organic hexahost: remarkable halogen-substitution effect on the handedness of water helix

Water helices surrounding the nano-channels of trichlorophloroglucinol and tribromophloroglucinol have different handedness, PMPMPM and PPPMMM (P = right-handed, M = left-handed), depending on halogenhalogen interactions between the host molecules.     

Utilization of 1-oxa-2,2-(dimesityl)silacyclopentane acetals in the stereoselective synthesis of polyols

We have developed a route for the stereoselective synthesis of 1-oxa-2,2-(dimesityl)silacyclopentane acetals, intermediates in the synthesis of highly functionalized 1,3-diols. This route involves a diastereoselective conjugate addition reaction of a hydrosilyl anion, a subsequent diastereoselective enolate alkylation, and a fluoride-catalyzed intramolecular hydrosilylation reaction to afford the oxasilacyclopentane acetal. A highly selective nucleophilic substitution reaction, followed by oxidation of the C-Si bond, leads to the desired polyol.     

Alkaloids of Liriodendron tulipifera

Tashkent Agricultural Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 587–588, July–August, 1991.     

Computer interactive identification system for polycyclic aromatic hydrocarbons in reversed-phase microcolumn liquid chromatography

Summary A computer interactive identification system is proposed which is based on the relationship between retention and molecular properties such as the size and shape of polycyclic aromatic hydrocarbons (PAHs). This system offers an automatic analytical process for liquid chromatography, providing a reliable identification of the separated components. The identification can be further enhanced by the use of multiple detectors such as a multichannel UV detector. The system can be used for optimization procedures, resulting in a highly automatic complex analytical system.