铜—氧气催化的氧化偶联反应研究

发布时间：2018-01-05 08:53

本文关键词：铜—氧气催化的氧化偶联反应研究　出处：《浙江大学》2017年博士论文　论文类型：学位论文

【摘要】：氧化偶联反应是近年来发展起来的新型偶联反应,不同于传统偶联反应需要亲电试剂的参与,其特点是在外加氧化剂条件下,通过氧化两种亲核性的底物使反应发生。直接使用碳氢化合物作为反应底物,在表观上脱除了两个氢原子,大大提高了反应的原子利用率。铜作为价格低廉、低毒性的催化剂,在氧化偶联反应机理上体现出经过自由基过程或形成类似钯催化的过渡金属有机中间体的过程,因此铜催化的有机反应具有独特的反应活性。此外,不论是何种价态的铜催化剂,通过路易斯酸相互作用和π-π协调作用都表现出与底物官能团较好的相容性。基于以上优点,铜催化的氧化偶联反应受到极高的关注和研究。另一方面,随着人们对可续续发展和绿色化学的日益重视,氧气作为环境友好、高原子经济性和来源广泛的氧化剂,是氧化偶联反应最理想的外加氧化剂。在氧化偶联反应的基础上,本论文主要围绕以铜为催化剂,氧气作为氧化剂的反应体系,系统发展了三类氧化偶联反应:铜-氧气参与S-N键偶联构筑苯磺酰胺及其衍生物的反应研究,铜-氧气催化α,α-双硫酚取代醛的合成研究,以及铜-氧气催化α-酰氧基酮的合成反应研究。铜-氧气参与S-N键偶联构筑苯磺酰胺及其衍生物的反应研究:在传统合成方法基础上,本部分以氯化亚铜作为催化剂,空气中氧气作为氧化剂,利用简单易得的苯硫酚为磺酰基来源,性质稳定的甲酰胺为氨基来源,通过生成磺酰基自由基实现了苯磺酰胺的一锅法合成。该方法对于不同苯硫酚底物具有广泛的适用性,对环状甲酰胺也有较好的反应效果。此外,通过一系列对照实验和验证试验,提出了可能的反应机理。铜-氧气催化α,α-双硫粉取代醛的合成研究:在总结金属催化和有机小分子催化的反应基础上,本部分直接使用脂肪族叔胺作为反应底物,以碘化亚铜为催化剂,氧气作为氧化剂,通过原位生成亚胺自由基阳离子,实现了 C(sp3)-S键的偶联。该反应体系对不同的脂肪族叔胺和苯硫酚具有广泛的适用性。通过X-射线单晶衍射确定了产物结构,并且通过捕获反应关键中间体和一系列控制实验,提出了可能的反应机理。铜-氧气催化α-酰氧基酮的合成反应研究:在传统合成方法基础上,本部分直接使用氧气作为绿色氧化剂,在碘化亚铜作为催化剂的体系下,实现了苯丙酮与羧酸的C(sp3)-O键偶联反应。该反应对苯甲酸衍生物、肉桂酸衍生物和部分有机小分子羧酸底物具有广泛的适用性,对不同酮衍生物也进行了考察。通过捕获反应关键中间体和对照试验,探究了铜在反应中的作用并提出了可能的反应机理。
[Abstract]:Oxidative coupling reaction is a new type of coupling reaction developed in recent years. It is different from the traditional coupling reaction which requires the participation of electrophilic reagent. The reaction takes place by oxidation of two nucleophilic substrates. Using hydrocarbons as reaction substrate, two hydrogen atoms are removed on the surface, and the atomic utilization ratio of the reaction is greatly improved. Copper is low in price. In the mechanism of oxidative coupling reaction, the low toxicity catalyst shows the process of free radical or the formation of transition metal organic intermediates similar to palladium catalysis. Therefore, the organic reaction catalyzed by copper has a unique activity. In addition, no matter what the valence of the copper catalyst. Both the Lewis acid interaction and 蟺-蟺 coordination show good compatibility with the functional groups of the substrate. Based on the above advantages, the oxidative coupling reaction catalyzed by copper has received great attention and research. On the other hand. With the increasing attention to sustainable development and green chemistry, oxygen as an environmentally friendly, high atomic economy and a wide range of sources of oxidants. On the basis of the oxidative coupling reaction, this paper focuses on the reaction system with copper as catalyst and oxygen as oxidant. Three kinds of oxidative coupling reactions were systematically developed: copper-oxygen reaction for S-N bond coupling of benzenesulfonamide and its derivatives, and copper-oxygen catalyzed synthesis of 伪, 伪 -dithiophenol substituted aldehydes. Studies on the synthesis of 伪 -acyloxyketone catalyzed by copper and oxygen. Studies on the synthesis of benzenesulfonamide and its derivatives by S-N bond coupling of copper and oxygen: based on the traditional synthesis methods. In this part, cuprous chloride was used as catalyst, oxygen in air as oxidant, phenylthiophenol as sulfonyl source and formamide as amino source. One pot synthesis of benzenesulfonamide was realized by generating sulfonyl radical. This method is widely applicable to different phenylthiophenol substrates and has good reaction effect to cyclic formamide. Through a series of controlled experiments and validation experiments, the possible reaction mechanism was put forward. The synthesis of 伪, 伪 -disulfide powder substituted aldehydes catalyzed by copper and oxygen: based on the summary of metal catalysis and organic small molecule catalysis. In this part, aliphatic tertiary amine was used as reaction substrate, copper iodide was used as catalyst and oxygen as oxidant to form imine radical cations in situ. The coupling of C _ p _ 3O _ 3-S bond was realized. The reaction system was widely applicable to different aliphatic tertiary amines and phenythiophenols. The structure of the product was determined by X-ray single crystal diffraction. The possible reaction mechanism was proposed by capturing the key intermediate and a series of control experiments. The synthesis of 伪 -acyloxyketone catalyzed by copper and oxygen: based on the traditional synthesis method. In this part, using oxygen as green oxidant and copper iodide as catalyst, the coupling reaction of phenylacetone with carboxylic acid Cnsp _ 3O bond was realized. The reaction was carried out by p-benzoic acid derivative. Cinnamic acid derivatives and some small organic carboxylic acid substrates are widely applicable. Different ketones derivatives are also investigated. The role of copper in the reaction was investigated and the possible reaction mechanism was proposed.
【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.251

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