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摘要：四取代烯烃广泛存在于天然产物、药物和生物活性分子中，此外，由于双键多样的反应性，使其成为重要的有机合成中间体。由于双键上的空间位阻很大，四取代烯烃的高效构建一直以来具有挑战性，是有机合成中的难点。砜基是常见的有机官能团，其广泛存在于生物活性分子以及杀菌剂和除草剂等农药中。因此C-S键的构建在有机合成中非常重要。在本论文中，我们以高炔丙醇作为原料，磺酰肼作为砜基源，实现了含有砜基的四取代烯烃的合成。该方法条件温和，绿色经济，操作简单，产物收率高。初步的机理研究表明，该反应可能经由砜基自由基对碳碳三键的加成和芳基的1,4-迁移等多个基元反应步骤。40960
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关键词：高炔丙醇；磺酰肼；砜基化；1,4-芳基迁移；四取代烯烃
Cascade Sulfonylation/1,4-aryl migration of homoallylic alcohols: a facile synthesis of tetrasubstituted olefins
Abstract：Tetrasubstituted olefin scaffolds are widely present in natural products, pharmaceuticals, and bioactive molecules. Furthermore, tetrasubstituted olefins are frequently used as important synthetic intermediates due to their perse reactivities. Because of the significantly steric hindrance around the C=C bond(s), the highly efficient construction of this type of compounds are formidable and challenging. Sulfone group, as a kind of common organic functional groups, has been frequently seen in many compounds with significant bioactivities, especially in some agrochemicals such as antifungals and herbicides. It is obvious that the introduction of C-S bonds is pretty important. In this dissertation, we achieved the synthesis of the tetrasubstituted olefins bearing a sulfone group with homoallylic alcohols as the starting material and with sulfonylhydrazine as the sulfonyl group source. This current method exhibits the following characteristics: mild conditions, green and cost-effective, simple operation, and high product yields. Preliminary mechanistic investigation has shown that this reaction likely proceeds via the addition of sulfonyl radical onto the C-C triple bond, subsequent 1,4-aryl migration, and other fundamental reaction steps.
Key words: homoallylic alcohols; sulfonylhydrazine, sulfonylation; 1,4-aryl migration; tetrasubstituted olefin
目 录
摘要…3
关键词3
Abstract…3
Key words3
1引言4
1.1砜基化合物的重要性4
1.2 四取代烯烃化合物的重要性… 4
1.3芳基迁移的研究进展简介 5
1.3.1 1,2-芳基迁移 … 5
1.3.2 1,4-芳基迁移 …6
2课题设计8
3材料和方法… 9
3.1仪器与试剂 9
3.2原料制备…10
4结果与讨论… 10
4.1 反应条件的优化 10
4.2 底物范围 …11
4.3 代表性化合物的相关表征数据12
5论文小结与展望13
致谢…14
参考文献 …15
附录 …16
高炔丙醇的砜基化/1,4-芳基迁移合成四取代烯烃的研究1 引言
1.1 砜基化合物的重要性
含有砜基的化合物在有机化学中占有重要的地位，其中包括砜类和磺酰胺类，这种化合物在农药和医药领域被广泛应用，它们通常具有广谱的生物活性，近年来越来越多的用于农用化学品（例如杀虫剂、杀菌剂等）和医药方面。由于其独特的化学结构和性质，烯基砜化合物通常具有某些重要的生物活性，例如，杀菌剂1[1]、氧化萎锈灵(Oxycarboxin) 2[2]和Falcipain-2抑制剂3[3]都含有烯基砜结构片段，此外，它们在有机合成中也是重要的中间体。
图1 含有烯基砜的生物活性分子