Synthesis of a new tricyclic 3-(tetrazol-5-yl)pyridine system from 2-(azidomethyl)nicotinonitriles

2-Methyl-3-cyanopyridines were converted into the corresponding 2-azidomethyl derivatives, which then underwent an intramolecular cycloaddition reaction. A novel heterocyclic system containing a 3-(tetrazol-5-yl)pyridine unit was obtained in this way.     

Click chemistry in materials synthesis. III. Metal‐adhesive polymers from Cu(I)‐catalyzed azide–alkyne cycloaddition

1,2,3‐Triazole‐based polymers generated from the Cu(I)‐catalyzed cycloaddition between multivalent azides and acetylenes are effective adhesive materials for metal surfaces. The adhesive capacities of candidate mixtures of azide and alkyne components were measured by a modified peel test, using a customized adhesive tester. A particularly effective tetravalent alkyne and trivalent azide combination was identified, giving exceptional strength that matches or exceeds the best commercial formulations. The addition of Cu catalyst was found to be important for the synthesis of stronger adhesive polymers when cured at room temperature. Heating also accelerated curing rates, but the maximum adhesive strengths achieved at both room temperature and high temperature were the same, suggesting that crosslinking reaches the same advanced point in all cases. Polytriazoles also form adhesives to aluminum, but copper is bound more effectively, presumably because active Cu(I) ions may be leached from the surface to promote crosslinking and adhesion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5182–5189, 2007     

Higher-order radiative perturbation theory

As a computationally effective tool, the first-order term of the radiative perturbation theory has been computed successfully, and has been applied in a number of areas. In this article, we develop the computational expressions for the higher-order terms of the perturbation expansion in a plane parallel atmosphere. These expressions are then implemented, and numerical results for some typical cases are presented. These results indicate that the computation is successful and that the higher-order terms are essential in cases where the first-order term alone cannot predict the perturbation with sufficient accuracy.     

Functionalized poly(oxanorbornene)‐block‐copolymers: Preparation via ROMP/click‐methodology

Block copolymers on basis of poly(oxanorbornenes) bearing functional moieties in their side‐chains are prepared via a combination of ROMP‐methods and 1,3‐dipolar‐“click”‐reactions. Starting from N‐substituted‐ω‐bromoalkyl‐oxanorbornenes and alkyl‐/perfluoroalkyl‐oxanorbornenes, block copolymers with molecular weights up to 25,000 g mol^?1 were generated. Subsequent nucleophilic exchange‐reactions yielded the block‐copolymers functionalized with ω‐azidoalkyl‐moieties in one block. The 1,3‐azide/alkine‐“click” reactions with a variety of terminal alkynes in the presence of a catalyst system consisting of tetrakis(acetonitrile)hexafluorophosphate copper(I) and tris(1‐benzyl‐5‐methyl‐1H‐ [1,2,3]triazol‐4‐ylmethyl)‐amine furnished the substituted block copolymers in high yields, as proven by NMR‐spectroscopy. The resulting polymers were investigated via temperature‐dependent SAXS‐methods, revealing their microphase separated structure as well as their temperature‐dependent behavior. The presented method offers the generation of a large set of different block‐copolymers from only a small set of starting materials because of the high versatility of the “click” reaction, thus enabling a simple and complete functionalization after the initial polymerization reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 485–499, 2007     

7-氮杂-3,6-二氧杂-二环[3.3.0]辛-2-酮类化合物合成的新方法

5-甲氧基-2-（5H）-呋喃酮与氮酸硅烷基酯通过1，3-偶极环加成反应可以为7-氮杂-4-甲氧基-3，6-二氧杂-二环[3.3.0]辛-2-酮类化合物提供新的合成途径。通过元素分析、IR、^1HNMR、^13CNMR、MS等波谱分析进行了结构表征。     

光诱导[2+2]环加成在有机合成中的应用

综述了烯烃、二烯、烯酮双键和烯烃的分子间或分子内光环加成,总结了过去二十五年在有机合成中的研究成果。     

The cycloaddition way to novel deoxy disaccharide analogs

A novel heterocycloaddition merges 2-thiono-3-ketolactones with carbohydrate glycals to afford materials which resemble disaccharides with an O-glycosidic linkage at the anomeric center and a thioether linking both C-2 and C-2′, thus creating a third heterocyclic ring. Upon desulfurization, these novel cycloadducts afford materials which are models for 2-deoxydisaccharides. Studies with two keto lactones and seven glycals are described.     

分子内环加成的甾体全合成

近年来,分子内环加成反应已广泛用于甾体化合物全合成,其主要一步是由取代的苯并环丁烯热裂而成的5,6-二亚甲基-1,3-环己二烯发生区域专一和立体选择性的环加成反应,构成甾体骨架。现在用此法已合成了一系列消旋和光学活性的甾体化合物。