EPR studies on some copper(II) complexes of 1,4,7,10-tetra-azadecane and its hexamethyl derivative

EPR studies have been carried out on solutions of the complexes [Cu(trien)NCS](NO₃), [Cu(trien)I]I, [Cu(Me₆trien)NCS]B?₄ and [Cu(Me₆trien)](ClO₄)₂, (trien = 1,4,7,10-tetraazadecane; Me₆trien = hexamethyl trien) in different solvents to investigate the solute-solvent interactions. From calculations of the 4s contribution in the ground state and bond parameters it is found that the axial bond in [Cu(trien)NCS](NO₃) dissolved in pyridine is weaker than that in the other complexes dissolved in different solvents. For the two methylated complexes, in spite of the +I effect of the methyl group, the in-plane copper-nitrogen bonds are found to be weak, which is probably due to the changes in structure caused by methylation.     

LiBF4-Catalyzed three-component coupling of an aldehyde, acetic anhydride and allyltrimethylsilane/TMSCN

Lithium tetrafluoroborate is found to be an efficient catalyst for allylation and cyanation of aldehydes with allyltrimethylsilane and trimethylsilyl cyanide in the presence of acetic anhydride at room temperature to produce homoallylic acetates and α-cyano acetates in excellent yields. A solution of 10 mol % of LiBF₄ in acetonitrile provides a convenient reaction medium to carry out allylation and cyanation reactions under very mild and neutral conditions.     

Characterization and reactivity of copper oxide catalysts supported on TiO2-ZrO2

A series of copper catalysts supported on TiO2-ZrO2 with copper loading varying from 1.0 to 21.6 wt % were prepared by a wet impregnation method. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy, electron spin resonance (ESR), temperature programmed reduction (TPR), and Brunauer-Emmett-Teller specific surface area measurements. Copper dispersion and metal area were determined by N2O decomposition by the passivation method. XRD results suggest that the copper oxide is present in a highly dispersed amorphous state at copper loadings <16.8 wt % in the sample and as a crystalline CuO phase at higher Cu loadings. Copper dispersion increases with Cu loading up to 5.1 wt % and levels off at higher loadings. The XPS peak intensity ratios of Cu 2p(3/2)/Ti 2p(3/2) and Cu 2p(3/2)/Zr 3d(5/2) were compared with the copper dispersion calculated from N2O decomposition. ESR results suggest the presence of two types of copper species on the TiO2-ZrO2 support. TPR profiles reveal the presence of highly dispersed copper oxide at lower temperatures and bulk CuO at higher temperatures. The catalytic properties were evaluated for the vapor-phase dehydrogenation of cyclohexanol to cyclohexanone and related to the dispersion of Cu on TiO2-ZrO2.     

A Novel,Chemoselective and Efficient Production of Amines from Azides Using ZrCl4/NaBH4

A practical & cheaper reagent system ZrCl₄/NaBH₄ is used for the production of amines from azldes is described.     

Reductive Cleavage of Acetals/Ketals with ZrCl4/NaBH4

Reductive cleavage of acetals/ketals with zirconium tetrachloride-sodium borohydride leading to the formation of ether alcohols is described.     

Enantioselective Synthesis of α‐Hydroxy Amides and β‐Amino Alcohols from α‐Keto Amides

Synthesis of enantiomerically enriched α‐hydroxy amides and β‐amino alcohols has been accomplished by enantioselective reduction of α‐keto amides with hydrosilanes. A series of α‐keto amides were reduced in the presence of chiral Cu^II/(S)‐DTBM‐SEGPHOS catalyst to give the corresponding optically active α‐hydroxy amides with excellent enantioselectivities by using (EtO)₃SiH as a reducing agent. Furthermore, a one‐pot complete reduction of both ketone and amide groups of α‐keto amides has been achieved using the same chiral copper catalyst followed by tetra‐n‐butylammonium fluoride (TBAF) catalyst in presence of (EtO)₃SiH to afford the corresponding chiral β‐amino alcohol derivatives.     

Free radical 5-exo-dig cyclization as the key step in the synthesis of bis-butyrolactone natural products: experimental and theoretical studies

Radical cyclization reactions were performed by 5-exo-dig mode to yield cis-fused bicyclic systems, leading to the synthesis of bis-butyrolactone class of natural products. The study was aimed at understanding the impact of alkyl side chains of furanoside ring systems in L-ara configuration on the radical cyclization. It was amply demonstrated by experimental studies that the increase in the length of the alkyl side chain has an effect on the cyclization: while efficient cyclization reactions could be realized with methyl and ethyl side chains, the yields were significantly reduced in the case of n-pentyl side chain. Theoretical studies using DFT and (RO)MP2 methods were carried out to analyze the influence of the substitution pattern on the cyclization barriers.     

Surface tension of water droplets at the critical radius

Zusammenfassung In die Theorie der homogenen Keimbildung wird für die Oberflächenspannung kleiner Tröpfchen eine vonTolman vorgeschlagene Korrektur eingeführt, die kleinere kritische Keimradien ergibt. Diese Verkleinerung ist zwar abhängig von Temperatur und Übersättigung, jedoch praktisch konstant oberhalb vierfacher Übersättigung. Die hier berechneten Werte kritischer Keimradien, der Molekülzahlen pro kritischen Keim, der Anzahl kritischer Keime sowie der Keimbildungsrate mit und ohne Korrektur sind in den Tabellen 1 und 2 dargestellt; Keimzahl und Keimbildungsrate sind zudem in Figur 1 für die Temperatur 283,2° K graphisch dargestellt. Um Vergleiche mit den Ergebnissen von Wolkenkammer-Versuchen anstellen zu können, wird der «Schwellenwert der Kondensation» neu definiert unter Einschluss des Korrekturterms; die so erhaltenen Werte sind in Tabelle 3 aufgeführt. Die Übereinstimmung mit dem Experiment ist besser als im Fall, in dem lediglich die Oberflächenspannung der ebenen Oberfläche in Rechnung gesetzt wird.

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This research was supported by Grant G-22292 (Cloud Physics Research) from the National Science Foundation.