General and practical catalytic enantioselective Strecker reaction of ketoimines: significant improvement through catalyst tuning by protic additives

Significant improvement in enantioselectivity and catalyst activity was achieved for the catalytic enantioselective Strecker reaction. Using a catalyst (1-2.5 mol %) prepared from Gd(OⁱPr)₃ and d-glucose derived ligand 1, and in the presence of 2,6-dimethylphenol as an additive, high enantioselectivity was obtained from a wide range of ketoimines, including heteroaromatic and cyclic ketoimines. The new method was applied to an efficient catalytic asymmetric synthesis of sorbinil, a therapeutic agent for diabetic complications.     

25-Alkoxy-26-benzoyloxycalix[4]arenes: the reaction mechanism of benzoyl migration

In the presence of K₂CO₃ as reaction base, the 25-alkoxy-27-benzoyloxy-calix[4]arenes were converted into 25-alkoxy-26-benzoyloxy derivatives by benzoyl-migration. A benzoyl-migrated reaction mechanism with a cyclic orthobenzoate-like intermediate was proposed, and the mechanism was supported by the identical reaction results on the conversion of 25-ethoxy-27-benzoyloxycalix[4]arene to 25-ethoxy-26-benzoyloxycalix[4]arene, and vice versa.     

Etude Des Propriétés Physico-Chimiques De ZnRb 4 (P 3 O 9 ) 2 ·6H 2 O

The dehydration of ZnRb 4 (P 3 O 9 ) 2 ·;6H 2 O was investigated, between 25 and 600°;C, by TG-DTA, X-ray diffraction, IR. It leads, between 300 and 500°;C, to a mixture of long chain polyphosphates RbPO 3 and ZnRb 2 (PO 3 ) 4 which stays stable until its melting point. The IR (1400-30 cm m 1 ) and Raman spectra (1400-100 cm m 1 ) of ZnRb 4 (P 3 O 9 ) 2 ·;6H 2 O are reported and assignments of fundamental modes proposed and compared with theoretical results obtained via the MNDO method for P 3 O 9 ring with C s symmetry. (La déshydratation, sous pression atmosphérique, du cyclotriphosphate ZnRb 4 (P 3 O 9 ) 2 ·;6H 2 O, a ét´;e effectuée, entre 25 and 600°;C, par spectrométrie IR, diffraction des rayons X, ATG et ATD. Elle conduit, entre 300 and 500°;C, au mélange de polyphosphates RbPO 3 et ZnRb 2 (PO 3 ) 4 qui reste stable jusqu'à la fusion. Les spectres vibrationnels IR (1400-30 cm m 1 ) et Raman (1400-100 cm m 1 ) du sel étudié ont été interprétés dans le domaine des vibrations de valence et de déformation du cycle P 3 O 9 et comparés avec les résultats des calculs théoriques par la méthode MNDO pour un cycle isolé de symétrie C s .)     

N,S-Substituted Dienes from Mono(arylthio)substituted- and S-, S,S-Substituted Dienes

Mono(thio)substituted dienes 1a-1b gave compounds 3a-c and 5d-g with piperazine and piperidine derivatives in dichloromethane. Compounds 8 , 9 , and 10 were obtained from the reactions of perchlorobutadiene ( 6 ) with 1,4-butanedithiol ( 7 ) in ethanol in the presence of sodium hydroxide. Compounds 12a-b , 13a-b were obtained from the reactions of perchlorobutadiene ( 6 ) with allylmercaptan (CH 2 =CH--CH 2 --SH) and mercaptoethanol (HO--CH 2 --CH 2 --SH).     

Sequential [2+2] Photocycloaddition and Rearrangement to Substituted Cyclopentanone. A formal Synthesis of Planococcyl Acetate

An extremely short synthesis of 2,2-dimethyl-3-hydroxymethyl cyclopentanone 2 (R¹ = R² = Me), an advanced intermediate in the synthesis of the pheromone planococcyl acetate 3, is described.     

Determination of the specific interaction of disubstituted aromatic compounds on hydrous zirconium oxide-loaded porous polymer resin

Summary A porous polymer resin loaded with hydrous zirconium oxide (Zr-gel) was evaluated as a stationary phase for the liquid chromatographic separation of disubstituted aromatic compounds. The prepared Zr-gel was used to separate disubstituted phenols andortho-substituted benzoic acid derivatives in reversed-phase mode. The retention time of catechol was greater than those of other disubstituted phenols; this implies that the Zr-gel has specificity for the phenolic hydroxyl group. The retention behavior ofortho-substituted benzoic acid derivatives on the Zr-gel was also evaluated in reversedphase mode using buffer. Phthalic acid was specifically retained in the vicinity of pH 6.0, which has been regarded as the equal adsorbic point. Similar behavior was also observed for salicylic acid, although the retention time of salicylic acid was less than that of phthalic acid. It seems that the specific retention behavior of hydrous zirconium oxide is a result of complexation with ligands such as hydroxyl and carboxyl groups. The results of this study have revealed that the retention mechanism of hydrous zirconium oxide is a combination of ion exchange and interaction based on complexation with ligands.     

Realtime control of robots with initial value perturbations via nonlinear programming methods

The mathematical model of an industrial robot with initial value perturbations is considered as a parametric nonlinear control problem subject to control and state constraints. Based on recent stability results for parametric control problems, a robust nonlinear programming method is proposed for computing the sensitivity derivatives of optimal solutions. Real-time control approximations of perturbed optimal solutions are obtained by evaluating a first order Taylor expansion of the perturbed solution. The efficiency of the real-time approximation is demonstrated for the robot model     

A statistical model for global optimization by means of select and clone

A statistical model tor giobai optimization is constructed generalizing some properties ofthe Wiener process to the multidimensional case. A new approach, which is similar to the Branch and Bound approach, is proposed to the construction of algorithms based on statistical models. A two dimensional version of the algorithm is implemented, and test results are presented     

Multivariate analysis using ‘and’ and ‘or’

The connectives ‘and’ and ‘or’ are potentially useful in multivariate analysis and theory construction. They are simple, logical ways to connect two or more variables together. However, until recently there has been no framework for operationalizing these connectives for continuous variables, and this lack has severely limited their use. Using fuzzy set theory as a basis for such a framework, this paper lays out the necessary tools and models to permit the use of ‘and’ and ‘or’ in multivariate analysis.Section 1 introduces conventional operators for ‘and’ and ‘or’, and Section 2 provides suitable extensions and generalizations of them. Section 3 sets out the required least-squares techniques for fitting these generalized operators to data, first in the context of ANOVA problems and then in regression contexts, for single-connective (three-variable) models. The theoretical developments and examples from real data-sets demonstrate the utility of ‘and’ and ‘or’ as a means to cell-specific interpretations of interaction effects which can also readily be translated into English. Section 4 extends these developments to multivariate, multiple-connective models and discusses issues of generalizability. The paper concludes (Section 5) with a brief discussion of remaining unsolved problems, future prospects for more sophisticated models, and computer programs.     

Infinite Quasimonotone Systems of Ordinary Differential Equations with Applications to Stochastic Processes

We deal with the initial value problem for countably infinite linear systems of ordinary differential equations of the form y '( t ) = A ( t ) y ( t ) where A ( t ) = ( a ij ( t ): i , j S 1) is a measurable, infinite and essentially positive matrix, i.e., a ij ( t ) S 0 for i p j . The main novelty of our approach is the systematic use of a classical comparison theorem for finite linear systems which leads easily to the existence of a nonnegative minimal solution and its properties. Application to generalized stochastic birth and death processes produces criteria for honest and dishonest probability distributions. A short proof of the Kolmogorov and Chapman-Kolmogorov equations for stochastic processes follows. The results hold for L 1 -coefficients. Our method extends to nonlinear infinite systems of quasimonotone type and can be used for numerical procedures that yield exact results; cf. the Addendum.