Kinetic resolution of secondary alcohols by the combination of a chiral Brønsted acid, DABCO, and acetyl chloride

An efficient and simple protocol for the kinetic resolution of secondary alcohols is presented. The new system is based on a combination of chiral Br?nsted acid, DABCO, and acetyl chloride and gives various enantioenriched alcohols with selectivity factors up to 105.     

Hg(OTf)2-catalyzed vinylogous semi-pinacol rearrangement leading to 1,4-dihydroquinolines

An efficient method for the construction of dihydroquinoline derivatives possessing a quaternary carbon center is developed by an application of Hg(OTf)(2)-catalyzed vinylogous semi-pinacol-type rearrangement. The reaction was found to be specifically catalyzed by mercury salt and to proceed via a bicyclic aminal.     

Potential clinical factors affecting hepatobiliary enhancement at Gd-EOB-DTPA-enhanced MR imaging

Objective

The objective was to clarify the clinical factors that might affect the degree of hepatic parenchymal enhancement at gadolinium ethoxybenzyl diethylenetriamine pentaacetic acid (Gd-EOB-DTPA)-enhanced magnetic resonance (MR) imaging.

Materials and Methods

A total of 84 patients with (n=63) and without chronic liver disease (n=21) underwent Gd-EOB-DTPA-enhanced MR imaging. Contrast-enhanced MR images of hepatobiliary phase (HP) were obtained at 20 min after Gd-EOB-DTPA administration. The relative enhancement (RE) of liver parenchyma at 20 min HP was calculated from region of interest measurements at each patient. Then, these results were correlated with various clinical parameters using Pearson correlation coefficient or Spearman rank correlation coefficient. Furthermore, the predictor of the degree of hepatic parenchymal enhancement was determined using multiple regression analysis.

Results

The presence or absence of chronic liver disease (P=.002), ascites (P=.005) and splenomegaly (P=.027), and the values of prothrombin activity (P=.008), total bilirubin (T-Bil) (P=.001), albumin (P=.001), aspartate aminotransferase (AST) (P=.002) and cholinesterase (P=.007) were significantly correlated with the RE of liver parenchyma at 20 min HP. Among these parameters, increases of T-Bil (P=.011 to .028) and AST (P=.018 to .049) were predictors of decreased hepatic parenchymal enhancement.

Conclusions

Hepatic parenchymal enhancement of Gd-EOB-DTPA was affected by various clinical parameters. Impaired hepatobiliary enhancement may be predicted by routine biochemical tests, such as T-Bil and AST.     

A light-induced phase exhibiting slow magnetic relaxation in a cyanide-bridged [Fe4Co2] complex

Single-molecule magnets: A cyanide-bridged hexanuclear complex showed a thermal electron-transfer-coupled spin transition centered at 220?K. Light irradiation at low temperature (LT; HT = high temperature) generated a metastable state showing slow magnetic relaxation in measurements of the alternating-current magnetic susceptibility (χ(m); see picture).     

The codes and the lattices of Hadamard matrices

It has been observed by Assmus and Key as a result of the complete classification of Hadamard matrices of order 24, that the extremality of the binary code of a Hadamard matrix H of order 24 is equivalent to the extremality of the ternary code of H^T. In this note, we present two proofs of this fact, neither of which depends on the classification. One is a consequence of a more general result on the minimum weight of the dual of the code of a Hadamard matrix. The other relates the lattices obtained from the binary code and the ternary code. Both proofs are presented in greater generality to include higher orders. In particular, the latter method is also used to show the equivalence of (i) the extremality of the ternary code, (ii) the extremality of the Z₄-code, and (iii) the extremality of a lattice obtained from a Hadamard matrix of order 48.     

Large Deviation Principle for Benedicks-Carleson Quadratic Maps

Since the pioneering works of Jakobson and Benedicks &; Carleson and others, it has been known that a positive measure set of quadratic maps admit invariant probability measures absolutely continuous with respect to Lebesgue. These measures allow one to statistically predict the asymptotic fate of Lebesgue almost every initial condition. Estimating fluctuations of empirical distributions before they settle to equilibrium requires a fairly good control over large parts of the phase space. We use the sub-exponential slow recurrence condition of Benedicks &; Carleson to build induced Markov maps of arbitrarily small scale and associated towers, to which the absolutely continuous measures can be lifted. These various lifts together enable us to obtain a control of recurrence that is sufficient to establish a level 2 large deviation principle, for the absolutely continuous measures. This result encompasses dynamics far from equilibrium, and thus significantly extends presently known local large deviations results for quadratic maps.     

Frequency response of sloshing in an annular cylindrical tank subjected to pitching excitation

Frequency responses of stable planar and rotary motions in a partially filled annular cylindrical tank, subjected to a pitching excitation at a frequency in the neighborhood of the lowest resonant frequency, are investigated. The nonlinearity of the liquid surface oscillation and the nonlinear coupling between the dominant modes and other modes (e.g., an axisymmetric mode) are considered in the response analysis of the sloshing motion. The basic equations of the liquid motion are derived by using the variational principle and the nonlinear equations of motion of the liquid surface displacement are formulated. The characteristics of the liquid motion in an annular cylindrical tank are discussed. The equations governing the amplitude of the stable planar and rotary liquid motions are derived and the stability of each motion is analyzed. An experiment was carried out using a model tank. It is shown that the nonlinear characteristic of the liquid motion in an annular cylindrical tank is more complicated than that in a circular cylindrical tank. Furthermore, it is shown that the nonlinear analysis is important for estimating the sloshing responses.     

Spin-crossover behavior and electrical conduction property in iron(II) complexes with tetrathiafulvalene moieties

Iron(II) complexes with neutral and oxidized tetrathiafulvalene (TTF) moieties were prepared and X-ray crystallographic analyses, magnetic and electrical resistivity measurements suggested an interaction of spin transition and electrical conductivity.     

Enzymatic epoxide-opening cascades catalyzed by a pair of epoxide hydrolases in the ionophore polyether biosynthesis

Our recent findings of the first epoxide hydrolase Lsd19, involved in lasalocid A biosynthesis, led us to investigate a long-standing controversial issue on the mechanism of enzymatic epoxide-opening cascades. The site-directed mutagenesis and domain dissection analysis to reveal the mechanism of the reaction catalyzed by Lsd19 is examined, especially in the role of acidic amino acid pair and catalytic domains.     

Application of α-alkoxy bridgehead radical for coupling of oxygenated carbocycles

A new coupling methodology for assembly of highly oxygenated carbocycles was developed. An α-alkoxy bridgehead radical was employed as the key reactive intermediate due to its potent reactivity, minimum steric interaction, and predestined stereochemical outcome. The radical of the trioxadamantane structure, generated from the O,Se-acetal, was reacted with electron-deficient cyclic olefins of various ring sizes. Intermolecular formation of sterically congested linkages between two tetrasubstituted carbons and application of the method to a three-component coupling were two significant achievements.