The silicon effect on the regioselectivity of the Tsuji-Trost reaction. Experimental and theoretical approaches

Regioselectivity of the Tsuji-Trost reaction on allyl acetates and carbonates substituted with silyl groups at the olefinic moiety has been analyzed. Silicon atom in the central carbon atom increases the stability of the intermediate π-allylpalladium cation with respect to the isomeric π-allylpalladium cation featuring the silicon in a terminal carbon atom.     

Asymmetric synthesis of abietane diterpenoids via B-alkyl Suzuki-Miyaura coupling. Formal total asymmetric synthesis of 12-deoxyroyleanone and cryptoquinone

A convergent synthetic strategy for abietane diterpenoids via B-alkyl Suzuki-Miyaura coupling and Lewis acid-mediated cyclization reactions is established. Asymmetric total synthesis of 12-deoxyroyleanone, an antileishmanial diterpene, is described.     

Expedient synthesis of villosin and its isomer (E)-labda-8(17),12,14-trien-15(16)-olide

The synthesis of the title compounds has been achieved in concise, highly regiocontrolled fashion from commercially available (+)-sclareolide. In addition, we offer evidence that the structure of a newly reported natural product from Zingiber ottensii is incorrect.     

Direct synthesis of Cbz-protected β-amino ketones by iodine-catalyzed three-component condensation of aldehydes, ketones and benzyl carbamate

Iodine has been found to be very effective catalyst for a Mannich reaction between an aryl aldehyde, an aryl ketone and benzyl carbamate, even though this is a less reactive amine, to produce Cbz-protected β-aryl β-amino carbonyl compounds in high yields.     

荷移分光光度法测定氨酪酸

氨酪酸(am inobutyric acid),化学名称为γ-氨基丁酸。本品在体内与血氨结合生成尿毒排出体外,有降低血氨及促进大脑新陈代谢的作用,能够增强葡萄糖磷酸酯化酶的活性,利于脑细胞功能的恢复。主要用于脑卒中后遗症、脑动脉硬化症、头部外伤后以及一氧化碳中毒所致昏迷的辅助治疗     

REM树脂的制备及亲核加成应用研究

用Mitsunobu反应及丙烯酰氯酰化反应制备了用于固相有机合成的载体REM树脂，将REM树脂与苄胺加成，考查了所合成REM树脂的反应性能，并通过元素分析测定氮含量，推出REM树脂的烯丙基固载量。利用所合成的REM树脂进行了与胺、酚的加成反应动力学研究。结果表明，REM树脂与脂肪族伯胺和促胺的加成反应能够进行，与苯胺不发生反应；REM树脂与酚不能发生亲核加成反应。     

Automatic detection and identification of shocks in Gaussian state‐space models: a Bayesian approach

An automatic monitoring and intervention algorithm that permits the supervision of very general aspects in an univariate linear Gaussian state–space model is proposed. The algorithm makes use of a model comparison and selection approach within a Bayesian framework. In addition, this algorithm incorporates the possibility of eliminating earlier interventions when subsequent evidence against them comes to light. Finally, the procedure is illustrated with two empirical examples taken from the literature. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis of substituted benzene derivatives by homo- and hetero-coupling of 2-bromobenzaldehyde and bromovinylaldehydes followed by McMurry coupling

A convenient synthetic approach to substituted benzene derivatives by modified Ullmann cross-coupling of 2-bromobenzaldehyde and bromovinylaldehydes followed by intramolecular McMurry coupling has been developed.     

钐(Ⅱ)类卡宾CH_3SmCH_2X(X=Cl、Br和Ⅰ)促进乙烯环丙烷化反应途径的理论研究(英文)

用密度泛函B3LYP方法研究了过渡金属钐类卡宾与乙烯的环丙烷化反应的机理。对三种不同的钐的SS试剂CH_3SmCH_2X(其中X=Cl、Br和Ⅰ)分别和CH_2CH_2反应的各反应物、中间体、过渡态和产物构型的全部结构几何参数进行了优化,用内禀反应坐标(IRC)计算和频率分析方法,对过渡态进行了验证。结果表明：CH_3SmCH_2X(其中X=Cl、Br和Ⅰ)与CH_2CH_2环丙烷化反应按亚甲基转移通道(通道A)和卡宾金属化通道(通道B)都可以进行,与锂类卡宾的反应机理相同,只是按亚甲基转移通道(通道A)进行反应较容易一些,而且此反应在较低的温度下就可以发生。     

分辨率为1pm的波长监测新方法

在亚毫米尺度金属包覆波导研究基础上，提出了一种波长监测的新方法.实验采用自由空间耦合技术，激发了波导中对波长变化十分灵敏的超高阶导模，并以此为探针，实现了1pm波长漂移的监测. 关键词： 波长监测 金属包覆波导 超高阶导模