大环二萜天然产物(±)-Mayol的全合成

西松烷型二萜类化合物是一大类广泛分布于松脂、烟草、陆地动物及海洋生物体中的具有十四元碳环骨架的化合物.其结构新颖复杂,且大多具有显著和广谱的生物活性.近几十年来,有关这类化合物的研究已引起了人们的极大兴趣.因此,开展这类天然产物及其类似物的全合成及构效关系的研究不仅具有重要的学术价值,而且具有潜在的应用前景.     

Keggin类杂多化合物催化α,β-不饱和羰基化合物环氧化

在乙睛溶剂中考察了一系列杂多化合物和过氧化氢水溶液催化的各种缺电子的α,β-不饱和羰基化合物的环氧化反应.在所研究的杂多化合物中,二缺位的[γ-SiW10(H2O)2O34](Bu4N)4显示出了最高的活性.     

Synthesis of Oxathiacrown Compounds by the Reactions of Sulfur Dichloride with Unsaturated Compounds and Their Extraction Characteristics. (Review)

Published data of the last 10-15 years on the use of the reactions of sulfur dichloride with various unsaturated compounds for the synthesis of oxathia- and thiacrown compounds and study of their extraction characteristics toward various transition and heavy metals are reviewed. Some previously unpublished results and associated experimental data are also included.     

锆氢化反应研究2.羰基化合物的选择性还原

本文对芳香醛和酮的锆氢化反应及水解产物进行了研究。产物经NMR证明为相应的醇。并以苯甲醛为代表,初步探讨了锆氢化反应的过程。还研究了含有其他官能团的苯甲醛对锆氢化反应选择性的影响,以及含有较大取代基酮类的锆氢化反应。     

Geometry,stability and aromaticity of β-diketiminate-coordinated alkaline-earth compounds

Alkaline-earth (Ae) metals have attracted a wealth of interdependent research from synthetic chemists. In Ae-catalyzed organometallic reactions, β-diketiminate is a typical ligand used to stabilize Ae catalysts by forming six-membered rings comprising Ae metals. Herein, studies focusing on the configuration of β-diketiminate-coordinated Ae compounds observed that the CC and CN bonds are homogeneous and unchanged. Furthermore, energetic studies observed that the formation of the Ae-incorporated six-membered rings results in enhanced stability of >20 kcal/mol. The nucleus-independent chemical shifts, anisotropy of the induced current density, and molecular orbital analyses demonstrated the non-aromaticity of the β-diketiminate-coordinated Ae compounds. The improved stability of these compounds can be explained by the delocalization of the π electrons derived from the β-diketiminate moiety.     

Synthesis of stereocontrolled α,α-difluoro-β-hydroxycarbonyl materials

Synthesis and synthetic utilities of stereocontrolled α,α-difluoro-β-hydroxy-γ,δ-unsaturated carbonyl compounds via enzymatic resolution with lipase PS (Pseudomonas cepacia, Amano Pharmaceutical Co. Ltd.) or lipase MY (Candida rugosa, Meito Sangyo Co. Ltd.) were described, and then the absolute configuration of obtained chiral materials was determined by the modified Mosher's method.     

Excess enthalpies of aqueous ternary solutions of urea and polyols at 25°C

The heats of dilution of nine ternary solutions of urea and polyols have been determined at 25°C. Excess enthalpies and their virial coefficients h _xy have been evaluated and compared with the data reported in the literature for mono- and polyfunctional alcohols and other oxygenated nonelectrolytes. The group additivity approach of Savage and Wood was applied and the contributions to the enthalpy coefficients, due to the water mediated interactions between urea and the functional groups –CH₂–, –OH, and –O– were determined. On the other hand, by using empirical combination rules among the cross- and self-enthalpic interaction coefficients it is possible to emphasize the large differences in the behavior (even in the presence of urea) of the polyols (and in particular of cyclitols) and of saccharides.     

Kinetic versus thermodynamic control during the formation of [2]rotaxanes by a dynamic template-directed clipping process

A template-directed dynamic clipping procedure has generated a library of nine [2]rotaxanes that have been formed from three dialkylammonium salts-acting as the dumbbell-shaped components-and three dynamic, imino bond-containing, [24]crown-8-like macrocycles-acting as the ring-shaped components-which are themselves assembled from three dialdehydes and one diamine. The rates of formation of these [2]rotaxanes differ dramatically, from minutes to days depending on the choice of dialkylammonium ion and dialdehyde, as do their thermodynamic stabilities. Generally, [2]rotaxanes formed by using 2,6-diformylpyridine as the dialdehyde component, or bis(3,5-bis(trifluoromethyl)benzyl)ammonium hexafluorophosphate as the dumbbell-shaped component, assembled the most rapidly. Those rotaxanes containing this particular electron-deficient dumbbell-shaped unit, or 2,5-diformylfuran units in the macroring, were the most stable thermodynamically. The relative thermodynamic stabilities of all nine of the [2]rotaxanes were determined by competition experiments that were monitored by (1)H NMR spectroscopy.