可见光催化烷基硼酸钾盐的偶联反应

发布时间：2018-06-04 06:12

本文选题：光化学 + 硼化学　；参考：《合肥工业大学》2017年硕士论文

【摘要】：烷基硼试剂是有机合成中重要且有用的结构基元。和传统的有机金属试剂(如烷基镁、锌、锡等试剂)相比,烷基硼试剂具有毒性低、易纯化以及对空气和水汽稳定等优点。有机硼试剂可以进行多种官能团反应。例如,可以将有机硼试剂转化成羟基、卤素、三氟甲基、三氟甲硫基、氨基等。我们当前的研究主要是通过光催化的手段发展一些烷基硼试剂的新偶联反应。腈类化合物不仅是重要的药物分子还是有机合成中的重要中间体,可以进一步转化成羧酸、酰胺、酯、胺等重要化合物。在此背景下,我们发展了可见光催化烷基硼酸钾盐脱硼腈基化反应。我们的新反应为一级、二级、三级烷基腈的合成提供了通用、高效、简便的方法。此外,使用的腈基化试剂是商业可得的无毒试剂:对甲基苯磺酰基腈(TsCN)。吡啶氮氧化物及其衍生物是组成生物活性分子和药物分子的重要结构单元之一。近年来,发展吡啶氮氧化物官能团化的新方法引起了人们更加广泛地重视。我们提出应用光催化的手段实现吡啶氮氧化物直接邻位选择性C-H烷基化反应。该反应使用简便易得的光催化剂并且具有很好的官能团兼容性。因而,当前的方法为邻位烷基取代的啶氮氧化物高效合成提供了新的路径。
[Abstract]:Alkyl boron reagent is an important and useful structural unit in organic synthesis. Compared with traditional organometallic reagents, such as alkyl magnesium, zinc and tin, alkyl boron reagents have the advantages of low toxicity, easy purification and stability to air and water vapor. Organic boron reagents can react with various functional groups. For example, organic boron reagents can be converted to hydroxyl, halogen, trifluoromethyl, amino, etc. Our current research is to develop some new coupling reactions of alkyl boron reagents by photocatalysis. Nitriles are not only important drug molecules but also important intermediates in organic synthesis. They can be further transformed into carboxylic acids, amides, esters, amines and other important compounds. In this context, visible light catalyzed alkyl borate potassium salt deboronitrile reaction was developed. Our new reaction provides a general, efficient and simple method for the synthesis of alkylonitrile of first, second and third order. In addition, the nitrile group reagent used is a commercially available nontoxic reagent: p-methylphenylsulfonyl nitrile (TsCNN). Pyridine nitrogen oxides and their derivatives are one of the important structural units of bioactive molecules and drug molecules. In recent years, more and more attention has been paid to the development of pyridine nitrogen oxide functionalization. The direct ortho-selective C-H alkylation of pyridine nitrogen oxides by photocatalysis is proposed. This reaction uses a simple and easy-to-get photocatalyst and has good functional compatibility. Therefore, the current method provides a new route for the efficient synthesis of o-alkyl substituted pyridine nitrogen oxides.
【学位授予单位】：合肥工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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