Friedel-Crafts alkylation of indoles with epoxides catalyzed by nanocrystalline titanium(IV) oxide

Friedel-Crafts alkylation of indoles with epoxides to afford 3-alkyl indole derivatives at room temperature with moderate to good yields and high regioselectivity using nanocrystalline titanium(IV) oxide catalyst is described.     

Synthesis of perfluoroheptanal by ozonolysis of perfluoro-1-octene

Perfluoro-1-octene was used as a model for developing a method for the preparative ozonolysis of perfluoro-1-alkenes to the corresponding perfluoro-nor-alkenals. Perfluoroheptanal was synthesized.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1146–1147, June, 1994.     

Preparation of silane-grafted pellets: silica bound reagents in a very convenient form

High surface area silica pellets are excellent supports for the preparation of silica supported reagents and solid-phase basal linkers through reaction with (RO)₃Si(CH₂)₃FG (FG=NH₂, NHMe, Cl, NHC(O)NH₂, OC(O)CMe(CH₂), NCO, NEt₂). High loadings (0.66-2.15 mmol g⁻¹) of grafted silane materials are realised at synthetically useful loadings per pellet (ca. 0.06 mmol). Preliminary trials show that trial linker chemistry and ligand synthesis can be carried out on these materials and that these reactions can be monitored by solid state ¹³C NMR studies on individual pellets.     

Concise asymmetric synthesis of (−)-halosaline and (2R,9aR)-(+)-2-hydroxy-quinolizidine by ruthenium-catalyzed ring-rearrangement metathesis

A ruthenium-catalyzed ring opening-ring closing metathesis reaction serves as the key step in the stereoselective synthesis of a new enantiopure 2-substituted-4,5-dehydropiperidine skeleton, a valuable intermediate for the synthesis of piperidine alkaloids (such as (−)-halosaline) and of hydroxylated quinolizidines (such as (2R,9aR)-(+)-2-hydroxy-quinolizidine).     

Triruthenium dodecacarbonyl/triphenylphosphine catalyzed dehydrogenation of primary and secondary alcohols

Dehydrogenation of alcohols into aldehydes and ketones by Ru₃(CO)₁₂/PPh₃ based homogeneous catalysis has been investigated as an alternative for the classical Oppenauer oxidation. Several catalytic systems have been screened in the Oppenauer-like oxidation of alcohols. A systematic study of various combinations of Ru₃(CO)₁₂, mono- and bidentate ligands and hydride acceptors was performed to enable dehydrogenation of primary alcohols to stop at the aldehyde stage. Among many H-acceptors screened, diphenylacetylene (tolane) proved the most suitable judged from its smooth reduction. Electron rich and deficient analogues of tolane have been synthesized and, based on competition experiments between these H-acceptors, a tentative catalytic cycle for the Ru₃(CO)₁₂/PPh₃-catalyzed dehydrogenations has been proposed.     

K＋－SrO－La_2O_3／ZnO催化剂上甲烷氧化偶联反应Ⅰ．催化活性和反应气中添加CO_2的影响

Ｋ＋┐ＳｒＯ┐Ｌａ２Ｏ３／ＺｎＯ催化剂上甲烷氧化偶联反应＊Ⅰ．催化活性和反应气中添加ＣＯ２的影响余林徐奕德＊＊郭燮贤（中国科学院大连化学物理研究所催化基础国家重点实验室，大连１１６０２３）关键词钾离子，氧化锶，氧化镧，氧化锌，金属氧化物催化剂，甲烷，...     

Synthesis of poly-yne polymers containing transition metals,disilane, disiloxane and phosphine groups in the main chain

The synthesis and characterization of metal poly-yne polymers containing disilane, disiloxane and phosphine groups in the main chain are described. The platinum and palladium poly-yne polymers were synthesized by polycondensation reactions between a metal chloride and an α, ω-bisethynyl complex in amines in the presence of cuprous iodide as a catalyst. The nickel poly-yne polymers were synthesized by an alkynyl ligand exchange reaction between a nickel acetylide and an α, ω-bisethynyl complex in diethylamine in the presence of cuprous iodide as a catalyst. The reaction of the platinum poly-yne polymer, containing disiloxane groups in the main chain, with copper (I) salts afforded adducts of η-²-bonded σ-acetylide polymer complexes. The reactions of the palladium poly-yne polymer, containing phosphine groups in the main chain, with transition-metal carbonyl complexes afforded polymer complexes which have phosphorus in the main chain-transition-metal bonds. A concentrated solution of the platinum poly-yne polymer containing disiloxane groups in the main chain forms a lyotropic liquid crystal in dichloromethane or 1, 2-dichloroethane.     

Synthesis and characterization of norbornene–ethylene–styrene terpolymers with a substituted ansa‐fluorenylamidodimethyltitanium‐based catalyst

This article reports a synthetic method for a norbornene–ethylene–styrene (N‐E‐S) terpolymer, which has not been well investigated so far, via incorporation of styrene (S) into vinyl‐type norbornene–ethylene (N‐E) copolymers catalyzed by a substituted ansa‐fluorenylamidodimethyltitanium [Me₂Si(3,6‐tBu₂Flu)(tBuN)]TiMe₂ catalyst ( I ) activated with a [Ph₃C][B(C₆F₅)₄]/Al(iBu)₃ cocatalyst at room temperature in toluene. The resulting terpolymerization product contained the targeted N‐E‐S terpolymer and the contaminated homopolymers, which were then able to be completely removed by solvent fractionation techniques. While homopolystyrene was easily extracted by fractionation with methylethylketone as a soluble part, homopolyethylene and a trace amount of homopolynorbornene could be perfectly separated by fractionation with chloroform as insoluble parts. The detail characterizations of a chloroform‐soluble polymer with gel permeation chromatography, nuclear magnetic resonance, and differential scanning calorimetry analyses proved that it contained a true N‐E‐S terpolymer with long N‐E sequences incorporated with isolated or short styrene sequences. The homogeneity of the morphology together with a single glass transition temperature that proportionally decreased with the increase of the styrene contents indicated that the N‐E‐S terpolymer obtained in this work is a random polymer with an amorphous structure. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2765–2773, 2007     

Palladium-catalyzed C-N bond formation: synthesis of 1-aryl-1H-pyrazoles from β-bromovinyl aldehydes and arylhydrazines

Cyclic and acyclic β-bromovinyl aldehydes are cyclized with an array of arylhydrazines in toluene at 125 °C in the presence of a palladium catalyst and a phosphorus chelating ligand together with NaO^tBu to give 1-aryl-1H-pyrazoles in moderate to good yields.     

A comparative XPS and UPS study of VOx layers on mineral TiO2(001)‐anatase supports

Four vanadium oxide layers on mineral TiO₂(001)‐anatase supports with different thickness (3–33 Å) were prepared with reactive d.c. magnetron sputtering and were extensively studied with photoelectron spectroscopy. Al Kα radiation and 150 eV synchrotron radiation were used as excitation sources. The evolution of the 2p, 3s and 3p core level line shapes of V and Ti as a function of the vanadium oxide thickness was studied, as well as the O1s and O2s core lines and the valence band. All the V2p spectra of the deposited vanadium oxide layers consist of at least 60% V⁵⁺, the rest being V⁴⁺. The V3p region is complicated by multiplet splitting, which prevents the determination of the vanadium oxidation state. The V3p multiplet splitting is different for the two excitation energies. No reduction of the titania support surface due to the vanadium oxide deposition was observed. Copyright © 2006 John Wiley & Sons, Ltd.