基于α-羰基二硫缩烯酮多米诺成环反应研究
摘要
随着当今自然资源的日益短缺和环境的不断恶化，可持续发展战略的实施已经刻不容缓。因此，发展高效的合成方法，从源头上消除或减少废物的排放是现代有机化学家们所面临的严峻挑战。而多米诺反应具有简单、高效、原子经济性高、无需分离中间产物、环境污染少等特点，迅速发展成为了有机化学中一个重要的热点研究领域。
本论文以发展高效、简洁的多米诺反应为基础，以实现简单高效的环合反应为核心，重点研究了具有两个1,5-双亲电体系结构的α-羰基二硫缩烯酮与各种偶极子双环化反应以及自由基导向的α-羰基二硫缩烯酮与二苯甲烷类化合物连续的分子间偶联和分子内环合反应。主要包括以下三方面内容:
在NaOH的作用下，利用具有1,5-双亲电体系结构的α-烯酰基二硫缩烯酮与甲基异腈类化合物进行连续的[5+1]环合和分子内[3+2]环合的多米诺双环化反应，成功制备了一系列氢化吲哚酮类化合物。该反应不仅具有合成路线简洁、反应条件温和以及高原子经济性和区域选择性等优点，而且在“一锅”反应中形成三个化学键和两个环。
以具有1,5-双亲电体系结构的α-烯酰基二硫缩烯酮为底物，在DBU的作用下，成功实现了其与重氮乙酸乙酯的双环化多米诺反应。该反应经历连续的1,3-偶极环加成/分子内的氮杂迈克尔加成/氧化芳构化的反应历程，创建了一种由简单易得的链状起始原料一步构建氢化吡咯并吡唑酮衍生物的合成新策略。
在DDQ的作用下，利用α-羰基二硫缩烯酮与二苯甲烷衍生物进行多米诺反应，实现了无金属催化下、自由基导向的α-羰基二硫缩烯酮α-位的官能化反应，即分子间烯烃Csp2–H键和无相邻杂原子的苄基Csp3–H键交叉脱氢偶联(CDC)反应。在此基础上，经过连续的分子间C(sp2)–C(sp3)键和分子内C(sp2)–C(sp2)键的双CDC反应过程，创建直接一步合成多取代茚类化合物的通用、简洁、高效的新方法。
With current the increasing shortage of natural resources and environmentworsening, implementing sustainable development has become essential. Hence, it isserious challenges for organic chemists to develop efficient synthesis methods whicheliminate or reduce emissions from the source. Domino reaction rapidly becomes oneof hot research areas in organic chemistry because of its advantage, such as simple,high efficiency, high atomic economy, without isolation of intermediate products, lowenvironmental pollution and so on.
In this thesis, based on the development of a highly efficient, simple dominoreaction, together with a core of achieving simple and efficient cyclization reaction,we mainly study the bicyclic reaction of α-oxo ketene dithioacetals containing double1,5-dielectrophilic systems and various dipoles as well as the radical-directed cascadeintermolecular coupling and intramolecular cyclization reaction of α-oxo ketenedithioacetals with diphenylmethane derivatives. This thesis mainly includes thefollowing three aspects:
A domino bicyclization reaction of α-alkenoyl ketene dithioacetals of1,5-dielectrophilic systems with methyl isocyanide derivatives has been developedand a series of hydrogenated indolones were obtained in the presence of NaOH. Thissingle step process involves a sequent [5+1] cycloaddition/intramolecular [3+2]cyclization where up to three chemical bonds and two rings are createdsimultaneously in one-pot. This protocol is associated with concise synthesis route,mild reaction conditions, high atom economy and regional selectivity.
A domino bicyclization reaction of the α-alkenoyl ketene dithioacetals with1,5-dielectrophilic systems with diazo compounds has been developed in the presenceof DBU. The reaction provides a highly efficient strategy for the direct synthesis of4H-pyrrolo[1,2-b]pyrazol derivatives through the tandem1,3-dipolarcycloaddition/intramolecular aza-Michael addition/oxidative aromatization reaction ofthe readily available acyclic precursors in single step.
A radical-directed α-functionalization of α-oxo ketene dithioacetals withdiphenylmethane derivatives has been carried out under metal-free conditions in thepresence of DDQ, namely the intermolecular cross-dehydrogenative coupling (CDC)reaction of Csp2–H bonds of alkenes with alkyl Csp3–H bonds not adjacent toheteroatoms. On this basis of this reaction, a new, general and highly efficient strategy for the direct synthesis of polysubstituted indene compounds has been developed via asequent intermolecular C(sp2)–C(sp3) bonds and intramolecular C(sp2)–C(sp2) bondscross-dehydrogenative coupling reactions in single step.
本论文以发展高效、简洁的多米诺反应为基础，以实现简单高效的环合反应为核心，重点研究了具有两个1,5-双亲电体系结构的α-羰基二硫缩烯酮与各种偶极子双环化反应以及自由基导向的α-羰基二硫缩烯酮与二苯甲烷类化合物连续的分子间偶联和分子内环合反应。主要包括以下三方面内容:
在NaOH的作用下，利用具有1,5-双亲电体系结构的α-烯酰基二硫缩烯酮与甲基异腈类化合物进行连续的[5+1]环合和分子内[3+2]环合的多米诺双环化反应，成功制备了一系列氢化吲哚酮类化合物。该反应不仅具有合成路线简洁、反应条件温和以及高原子经济性和区域选择性等优点，而且在“一锅”反应中形成三个化学键和两个环。
以具有1,5-双亲电体系结构的α-烯酰基二硫缩烯酮为底物，在DBU的作用下，成功实现了其与重氮乙酸乙酯的双环化多米诺反应。该反应经历连续的1,3-偶极环加成/分子内的氮杂迈克尔加成/氧化芳构化的反应历程，创建了一种由简单易得的链状起始原料一步构建氢化吡咯并吡唑酮衍生物的合成新策略。
在DDQ的作用下，利用α-羰基二硫缩烯酮与二苯甲烷衍生物进行多米诺反应，实现了无金属催化下、自由基导向的α-羰基二硫缩烯酮α-位的官能化反应，即分子间烯烃Csp2–H键和无相邻杂原子的苄基Csp3–H键交叉脱氢偶联(CDC)反应。在此基础上，经过连续的分子间C(sp2)–C(sp3)键和分子内C(sp2)–C(sp2)键的双CDC反应过程，创建直接一步合成多取代茚类化合物的通用、简洁、高效的新方法。
With current the increasing shortage of natural resources and environmentworsening, implementing sustainable development has become essential. Hence, it isserious challenges for organic chemists to develop efficient synthesis methods whicheliminate or reduce emissions from the source. Domino reaction rapidly becomes oneof hot research areas in organic chemistry because of its advantage, such as simple,high efficiency, high atomic economy, without isolation of intermediate products, lowenvironmental pollution and so on.
In this thesis, based on the development of a highly efficient, simple dominoreaction, together with a core of achieving simple and efficient cyclization reaction,we mainly study the bicyclic reaction of α-oxo ketene dithioacetals containing double1,5-dielectrophilic systems and various dipoles as well as the radical-directed cascadeintermolecular coupling and intramolecular cyclization reaction of α-oxo ketenedithioacetals with diphenylmethane derivatives. This thesis mainly includes thefollowing three aspects:
A domino bicyclization reaction of α-alkenoyl ketene dithioacetals of1,5-dielectrophilic systems with methyl isocyanide derivatives has been developedand a series of hydrogenated indolones were obtained in the presence of NaOH. Thissingle step process involves a sequent [5+1] cycloaddition/intramolecular [3+2]cyclization where up to three chemical bonds and two rings are createdsimultaneously in one-pot. This protocol is associated with concise synthesis route,mild reaction conditions, high atom economy and regional selectivity.
A domino bicyclization reaction of the α-alkenoyl ketene dithioacetals with1,5-dielectrophilic systems with diazo compounds has been developed in the presenceof DBU. The reaction provides a highly efficient strategy for the direct synthesis of4H-pyrrolo[1,2-b]pyrazol derivatives through the tandem1,3-dipolarcycloaddition/intramolecular aza-Michael addition/oxidative aromatization reaction ofthe readily available acyclic precursors in single step.
A radical-directed α-functionalization of α-oxo ketene dithioacetals withdiphenylmethane derivatives has been carried out under metal-free conditions in thepresence of DDQ, namely the intermolecular cross-dehydrogenative coupling (CDC)reaction of Csp2–H bonds of alkenes with alkyl Csp3–H bonds not adjacent toheteroatoms. On this basis of this reaction, a new, general and highly efficient strategy for the direct synthesis of polysubstituted indene compounds has been developed via asequent intermolecular C(sp2)–C(sp3) bonds and intramolecular C(sp2)–C(sp2) bondscross-dehydrogenative coupling reactions in single step.
引文
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