α-羟基二硫缩烯酮的合成及应用研究
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摘要
α-羰基二硫缩烯酮是一类重要的有机合成中间体。自从1910年由Kelber首次合成以来,经过近百年的发展已经成为有机合成化学的研究热点之一。官能团的多样性这一结构特点和烷硫基的空间电子效应赋予了该类化合物化学反应的多样性,既可以与亲电试剂又可以和亲核试剂发生反应。利用该中间体可以合成许多具有特殊结构的化合物,广泛地应用于有机合成和天然产物的合成中。
α-羟基二硫缩烯酮是由α-羰基二硫缩烯酮经还原制得的,该类化合物易于制备,具有多个反应中心。从结构上看,α-羟基二硫缩烯酮属于烯丙型的醇,由于受到双烷硫基的强供电子作用,更易在α位形成稳定的碳正离子,可以与亲核体发生亲核取代等反应。此外,受到α’-位官能团及烷硫基变化的影响,α-羟基二硫缩烯酮的性质也会产生明显的变化。因此,α-羟基二硫缩烯酮的合成及其在有机合成中的应用是一个重要的研究课题。
本课题组从事α-羰基二硫缩烯酮化学的研究已经有十几年的时间,在研究积淀的基础之上本论文利用合成设计,以α-羟基二硫缩烯酮的合成为工作基础,探索了α-羟基二硫缩烯酮发生的一系列基本反应,例如Ritter反应、碳碳键偶联反应、脱水反应和醚化反应,并以这些反应为基础,分别发展了合成多取代六元含氮、含氧杂环化合物的新方法。论文工作主要包括以下4个方面的内容:
1.设计合成了α-乙酰基二硫缩烯酮化合物,然后经过还原反应,制备了一系列α-羟基二硫缩烯酮类化合物。
2.研究了α-羟基二硫缩烯酮发生的一系列基本反应,包括Ritter反应;与活泼亚甲基化合物和活化烯烃的偶联反应;脱水反应和与醇脱水成醚反应等。
3.以与活泼亚甲基化合物的偶联反应为基础,利用偶联产物--多羰基二硫缩烯酮合成了3,4-二氢-2-吡啶酮类化合物。
4.研究了α-烯酰基二硫缩烯酮经还原一步分子内成环的反应,制得了δ-内酯类化合物。
α-Oxo ketenedithioacetals are a kind of versatile intermediates in organic synthesis. Since Kelber first synthesized in 1910,α-oxo ketene-(S,S)-acetals chemistry has become a hot spot in organic chemistry research through the development of about one hundred years. It can be used in many reactions for their functional group multiplicity and special stereoelectronic effect from the alkylthio functionalities, react not only with electrophilic reagent but also with nucleophilic reagent. It can construct many compounds with special structures and can be applied in organic synthesis and the composition of natural products.
α-Hydroxy ketene-(S,S)-acetals, synthesized byα-oxo ketenedithioacetals which is reducted, is easier to prepare and bear much more functionalities. From the view of structure,α-hydroxy ketene-(S,S)-acetals belong to allylic alcohol. Because of receiving the affection of strong supplies electron from the alkylthio functionalities,α-hydroxy ketene-(S,S)-acetals form stable carbon cation easily atαposition and carry on nucleophilic substitution reaction with nucleophilic reagent. In addition, received the affection of changes from functionalities atα′position and alkylthio functionalities, the nature ofα-hydroxy ketene-(S,S)-acetals also change remarkably. Therefore, studies on the synthesis and the applications ofα-hydroxy ketene-(S,S)-acetals should be a valuable research project.
Based on the research achievements of our group inα-oxo ketene-(S,S)-acetal chemistry in the past several years, my thesis under synthetic design, taking the synthesis of newα-hydroxy ketene-(S,S)-acetals as foundation, explores a series of basic reactions whichα-hydroxy ketene-(S,S)-acetals can react, such as Ritter reaction、C-C bond-forming reaction、Dehydration reaction and Etherification reaction, and based on these basic reactions, we also carried out on the new synthetic methodologies for oxygen-, nitrogen-containing heterocycles. The contents in this thesis mainly include four aspects:
1. Design and synthesisα-Oxo ketenedithioacetals, prepared a series ofα-hydroxy ketene-(S,S)-acetals by reduction.
2. Study a series of basic reactions whichα-hydroxy ketene-(S,S)-acetals can react, including Ritter reaction with acetonitrile、C-C bond-forming reaction with active methylene compounds and activated alkenes、Dehydration reaction and Etherification reaction with alcohol.
3. Base on C-C bond-forming reaction with active methylene compounds, used coupling products—polycarbonyl compounds to synthesis 3,4-dihydropyridin-2(1H)-ones.
4. Study one-step intramolecular ring-closure reaction ofα-alkenoyl ketene-(S,S)-acetals by reduction and synthesis type ofδ-lactones compounds.
α-羟基二硫缩烯酮是由α-羰基二硫缩烯酮经还原制得的,该类化合物易于制备,具有多个反应中心。从结构上看,α-羟基二硫缩烯酮属于烯丙型的醇,由于受到双烷硫基的强供电子作用,更易在α位形成稳定的碳正离子,可以与亲核体发生亲核取代等反应。此外,受到α’-位官能团及烷硫基变化的影响,α-羟基二硫缩烯酮的性质也会产生明显的变化。因此,α-羟基二硫缩烯酮的合成及其在有机合成中的应用是一个重要的研究课题。
本课题组从事α-羰基二硫缩烯酮化学的研究已经有十几年的时间,在研究积淀的基础之上本论文利用合成设计,以α-羟基二硫缩烯酮的合成为工作基础,探索了α-羟基二硫缩烯酮发生的一系列基本反应,例如Ritter反应、碳碳键偶联反应、脱水反应和醚化反应,并以这些反应为基础,分别发展了合成多取代六元含氮、含氧杂环化合物的新方法。论文工作主要包括以下4个方面的内容:
1.设计合成了α-乙酰基二硫缩烯酮化合物,然后经过还原反应,制备了一系列α-羟基二硫缩烯酮类化合物。
2.研究了α-羟基二硫缩烯酮发生的一系列基本反应,包括Ritter反应;与活泼亚甲基化合物和活化烯烃的偶联反应;脱水反应和与醇脱水成醚反应等。
3.以与活泼亚甲基化合物的偶联反应为基础,利用偶联产物--多羰基二硫缩烯酮合成了3,4-二氢-2-吡啶酮类化合物。
4.研究了α-烯酰基二硫缩烯酮经还原一步分子内成环的反应,制得了δ-内酯类化合物。
α-Oxo ketenedithioacetals are a kind of versatile intermediates in organic synthesis. Since Kelber first synthesized in 1910,α-oxo ketene-(S,S)-acetals chemistry has become a hot spot in organic chemistry research through the development of about one hundred years. It can be used in many reactions for their functional group multiplicity and special stereoelectronic effect from the alkylthio functionalities, react not only with electrophilic reagent but also with nucleophilic reagent. It can construct many compounds with special structures and can be applied in organic synthesis and the composition of natural products.
α-Hydroxy ketene-(S,S)-acetals, synthesized byα-oxo ketenedithioacetals which is reducted, is easier to prepare and bear much more functionalities. From the view of structure,α-hydroxy ketene-(S,S)-acetals belong to allylic alcohol. Because of receiving the affection of strong supplies electron from the alkylthio functionalities,α-hydroxy ketene-(S,S)-acetals form stable carbon cation easily atαposition and carry on nucleophilic substitution reaction with nucleophilic reagent. In addition, received the affection of changes from functionalities atα′position and alkylthio functionalities, the nature ofα-hydroxy ketene-(S,S)-acetals also change remarkably. Therefore, studies on the synthesis and the applications ofα-hydroxy ketene-(S,S)-acetals should be a valuable research project.
Based on the research achievements of our group inα-oxo ketene-(S,S)-acetal chemistry in the past several years, my thesis under synthetic design, taking the synthesis of newα-hydroxy ketene-(S,S)-acetals as foundation, explores a series of basic reactions whichα-hydroxy ketene-(S,S)-acetals can react, such as Ritter reaction、C-C bond-forming reaction、Dehydration reaction and Etherification reaction, and based on these basic reactions, we also carried out on the new synthetic methodologies for oxygen-, nitrogen-containing heterocycles. The contents in this thesis mainly include four aspects:
1. Design and synthesisα-Oxo ketenedithioacetals, prepared a series ofα-hydroxy ketene-(S,S)-acetals by reduction.
2. Study a series of basic reactions whichα-hydroxy ketene-(S,S)-acetals can react, including Ritter reaction with acetonitrile、C-C bond-forming reaction with active methylene compounds and activated alkenes、Dehydration reaction and Etherification reaction with alcohol.
3. Base on C-C bond-forming reaction with active methylene compounds, used coupling products—polycarbonyl compounds to synthesis 3,4-dihydropyridin-2(1H)-ones.
4. Study one-step intramolecular ring-closure reaction ofα-alkenoyl ketene-(S,S)-acetals by reduction and synthesis type ofδ-lactones compounds.
引文
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