We have developed a new class of pyridine catalyst for asymmetric acylation of sec-alcohols having a conformation switch system in which interconversion between self-complexation and uncomplexation is induced by acylation and deacylation steps, respectively. Kinetic resolution of various sec-alcohols is performed by the asymmetric acylation with isobutyric anhydride using 0.05 to 0.5 mol % catalyst 1a with s values of up to 30. In addition, dl-diols are also resolved in a similar manner in good selectivity. Moreover, asymmetric desymmetrization of meso-1,X-diols (X = 2-6) are achieved in the presence of 0.5-5 mol % catalyst 1a. A working model for the reaction mechanism is proposed on the basis of the (1)H NMR measurements, X-ray structural analyses, and AM1 and DFT calculations, where the conformation switch system governed by an intramolecular cation-pi interaction between a pyridinium ring and a thiocarbonyl group would play a key role to attain both good selectivity and high catalytic activity. 相似文献
A new water soluble palladium(II) complex (2) derived from N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine (edteH4) (1) was synthesized in high yield and characterized by 1H, 13C, HMQC and COSY NMR spectroscopy. X-ray diffraction studies on a single crystal of 2 confirmed the cis square planar geometry; the edteH4 ligand (1) is κ2 (N,N)-coordinated with four pendant CH2CH2OH groups. This new complex [PdCl2(edteH4)] (2) and the previously synthesized triethanolamine complex [Pd(OCH2CH2N(CH2CH2OH)2)2] (3) were tested as catalysts for the Suzuki/Miyaura cross-coupling reaction of various aryl bromides with phenylboronic acid in water. Electronically activated aryl bromides, such as 4-bromoacetophenone and 4-bromobenzaldehyde undergo the cross-coupling with extremely high turnover numbers (TON) of up to 1,00,000 without organic solvent. 相似文献
X-ray diffraction measurements for the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF4], mixed with CO2 were carried out at high pressures using our developed polymer cell. The intermolecular distribution functions obtained for [BMIM][BF4]–CO2 mixtures showed that CO2 molecules are preferentially solvated to the [BF4]− anion. The similar preferential solvation was previously observed in analogous 1-btuyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], with a different anion, which is in harmony with the present results in [BMIM][BF4]–CO2. 相似文献
We consider the problem of constructing functional regression models for scalar responses and functional predictors, using
Gaussian basis functions along with the technique of regularization. An advantage of our regularized Gaussian basis expansions
to functional data analysis is that it creates a much more flexible instrument for transforming each individual’s observations
into functional form. In constructing functional regression models there remains the problem of how to determine the number
of basis functions and an appropriate value of a regularization parameter. We present model selection criteria for evaluating
models estimated by the method of regularization in the context of functional regression models. The proposed functional regression
models are applied to Canadian temperature data. Monte Carlo simulations are conducted to examine the efficiency of our modeling
strategies. The simulation results show that the proposed procedure performs well especially in terms of flexibility and stable
estimates. 相似文献
DNA duplexes containing 5‐modified uracil pairs (5‐bromo, 5‐fluoro, and 5‐cyanouracil) bind selectivity to metal ions. Their selectivity is sensitive to the pH value of the solution (see picture), as the acidities of the modified uracil bases vary according to the electron‐withdrawing properties of the substituents.
The effect of Ph‐OH group content on gelation time, mechanical properties, hydrophobicity, and cellular adhesiveness of hydrogels produced from carboxymethylcellulose derivatives is investigated. A higher Ph‐OH group content induces faster gelation and yields more brittle and hydrophobic gels. After 4 h of seeding, a larger number of L929 fibroblasts adhere to the hydrogel of the CMC‐Ph that contains 15.4 Ph‐OH groups per 100 repeat units of uronic acid (97% adhesion rate) than to the gel of CMC‐Ph with only 8.4 Ph‐OH groups (62% adhesion rate). The results demonstrate that controlling the Ph‐OH group content is an effective and useful way to control cellular adhesion and proliferation on the hydrogels, as well as gelation time and mechanical properties of the gels.