Synthesis of allyl and alkyl vinyl ethers using an in situ prepared air-stable palladium catalyst. Efficient transfer vinylation of primary,secondary, and tertiary alcohols

An air-stable palladium catalyst formed in situ from commercially available components efficiently catalyzed the transfer vinylation between butyl vinyl ether and various allyl and alkyl alcohols to give the corresponding allyl and alkyl vinyl ethers in 61-98% yield in a single step.     

A catalytic synthesis of thiosilanes and silthianes: palladium nanoparticle-mediated cross-coupling of silanes with thio phenyl and thio vinyl ethers through selective carbon-sulfur bond activation

Palladium nanoparticles generated in situ from N,N-dimethyl-acetamide (DMA) solutions of PdX(2) (X = Cl(-), OAc(-), OCOCF(3)(-)) or Pd(2)(dba)(3) by reduction with alkyl silanes R(3)SiH (R = Me, Et, i-Pr, t-Bu) are selective catalysts for the cross-coupling of the silanes R(3)SiH with phenyl and vinyl thioethers forming the corresponding thiosilanes and silthianes in high yields and under mild conditions. The method is applicable to phenyl thioglycosides, giving access to thiosilyl glycosides a new class of sugar derivatives.     

On the Homeomorphism Groups of Cantor's Discontinuum and the Spaces of Rational and Irrational Numbers

The paper shows that the homeomorphism groups of, respectively,Cantor's discontinuum, the rationals and the irrationals haveuncountable cofinality. It is well known that the homeomorphismgroup of Cantor's discontinuum is isomorphic to the automorphismgroup Aut B of the countable, atomless boolean algebra B. Soalso Aut B has uncountable cofinality, which answers a questionposed earlier by the first author and H. D. Macpherson. Thecofinality of a group G is the cardinality of the length ofa shortest chain of proper subgroups terminating at G. 2000Mathematics Subject Classification 20B22, 20E15.     

Regioselective silylation of sugars through palladium nanoparticle-catalyzed silane alcoholysis

Palladium(0)-catalyzed silane alcoholysis was applied to sugars for the first time using tert-butyldimethylsilane (TBDMS-H) and Ph(3)SiH as the silanes. The catalyst is a colloidal solution of Pd(0) generated in situ from PdX(2) (X = Cl(-), OAc(-)) and TBDMS-H in N,N-dimethylacetamide. The colloid has been characterized by dynamic light scattering and transmission electron microscopy and consists of catalytically highly active nanoparticles of approximately 2 nm diameter. The silane alcoholysis reaction is an effective method for the regioselective silylation of methyl and phenyl glycosides and generates hydrogen gas as the only side product. For many of the sugar substrates investigated, the distribution of regioisomers obtained is complementary to that of the traditional R(3)SiCl/base (base = pyridine, imidazole) methodology and gives convenient access to the 3,6- rather than the 2,6-silylated pyranosides, obtained as the main product by the silyl chloride method. The method also allows a selective axial silylation of levoglucosan and 1,3,5-O-methylidene-myo-inositol. In an attempt to rationalize the observed regioselectivities, ab initio predictions (HF/3-21G) have been made on the relative energies of some of the silylated products. They suggest that the observed regioselectivities do not reflect a kinetic vs thermodynamic product distribution but are induced by the silylation agent employed. Models for the possible origin of the observed regioselectivity in both silylation methods (silane- and silyl chloride-based) are discussed.     

Nonparametric Statistical Methods and the Pricing of Derivative Securities

In this review paper we summarise several nonparametric methods recently applied to the pricing of financial options. After a short introduction to martingale-based option pricing theory, we focus on two possible fields of application for nonparametric methods: the estimation of risk-neutral probabilities and the estimation of the dynamics of the underlying instruments in order to construct an internally consistent model.     

Selective deoxygenation of sugar polyols to alpha,omega-diols and other oxygen content reduced materials--a new challenge to homogeneous ionic hydrogenation and hydrogenolysis catalysis

An oxygen atom on every carbon--this is the problem! While nature provides linear C(3) to C(6) building blocks in the form of sugar alcohols in large and renewable abundance, they are overfunctionalized for the purpose of most chemical applications. Selective deoxygenation by anthropogenic catalyst systems may be one answer to this challenge.     

Selbstorganisation von Chinodimethanen über kovalente Bindungen,Mitteilung III,Untersuchungen zur Herstellung von Nanostrukturen

Self‐Assembly of Quinodimethanes through Covalent Bonds. Part III. Investigations on the Preparation of Nanostructures As part of our studies on the tetramerization of quinodimethane 1 to the macrocyclic compound 2 , the influence of substituents on this reaction was investigated. It was found that a large range of substituents such as 2‐phenylethyl, 2‐(4‐methoxyphenyl)ethyl, 2‐(4‐fluorophenyl)ethyl, 2‐[4‐(tert‐butyl)phenyl]ethyl, and 2‐[4‐(2‐phenylethyl)phenyl]ethyl, attached at positions 2 and 7 of 9H‐fluorene, do not prevent the tetramerization. The key step in the formation of the macrocylic compounds 13a – e is the debromination of 12a – e with mercury to the corresponding quinodimethanes which undergo a self‐assembly forming 13a – e in high yields. To study the conjugative influence of substituents on tetramerization, the effect of the hex‐1‐ynyl groups at positions 3 and 6 of the 9H‐fluorene rings was investigated. In this case, the corresponding macrocycle 17 was generated by the reaction of diol 16a with SnCl₂. Although the expected tetramerization to 17 occurred, the yield was lower than in the case of 13a – e , due to the sensitivity of the product.     

Selbstorganisation von Molekülen über kovalente Bindungen: Selektive Tetramerisierung eines p-Chinodimethans

Self-Organization of Molecules by Covalent Bonds: Selective Tetramerization of a p -Quinodimethane A simple and efficient synthesis of paracyclophane derivatives based on self-organization of a quinodimethane is described. Treatment of dibromides 5a – d with mercury afforded in high yield the macrocyclic compounds 6a – d . Interestingly, these compounds change the color on grinding and heating, from colorless to violet. The structure of 6a – d was determined by spectroscopic analyses. Single-crystal structure analysis of 6b and 6c confirmed the proposed structure.