基于甲基异腈合成2-酰基吡咯及并环吡咯的多米诺反应研究
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摘要
吡咯是一类非常重要的杂环化合物，众多药物、天然产物和合成材料中都含有吡咯结构单元，因此，在过去一个世纪以来，吡咯及其衍生物的合成一直是有机合成化学的研究热点。尽管如此，通过使用廉价易得的原料，简洁、高效地构筑结构多样性的吡咯衍生物的新合成策略仍然倍受关注。
本论文通过发展新颖、高效的多米诺反应，为多取代吡咯、并环吡咯及吲哚里西啶化合物提供新合成策略。所采用的方法具有原料易得、反应条件温和、产物结构多样化、反应步骤经济性高等优点。同时，对反应机理进行了深入细致的研究。
论文共分六个章节。第一章综述了多米诺反应、基于甲基异腈的杂环化反应及吡咯合成的研究进展。第二章提出了本论文的选题依据。
第三章研究了在温和条件下，无需过渡金属催化，高效，原子经济性地一步合成多取代环戊烷并吡咯化合物的新合成策略。该多米诺反应首次实现了分子内γ-位碳亲电体捕捉原位生成的亚胺负离子，成功地使异腈的端碳连续发生两次反应，构建了两个C–Cσ键。
第四章发展了α,β-不饱和酮和对甲苯磺酰基甲基异腈的串联Michael加成/异氰对C–C键插入反应，为多取代2-酰基吡咯化合物提供简洁、高效的合成方法。首次实现了分子内α-位碳亲电体捕捉原位生成的亚胺负离子。
第五章通过环状α,β-不饱和酮与对甲苯磺酰甲基异腈的串联Michael加成/异氰对C–C键插入反应，在构建吡咯环的同时通过C–C键插入形成苯并吲哚二酮及七/八元并环吡咯化合物。
第六章，在碱催化下，首次实现了通过非环状前体—-双烯酰基二硫缩烯酮与甲基异腈的新型串联[7+1]环加成/分子内环化反应，高产率、高非对映选择性、高原子经济性地构筑了氮杂八元双环化合物和含有六个相邻手性中心的吲哚里西啶衍生物，实现了在无过渡金属催化条件下的中环化合物的合成。
Pyrroles are an important class of heterocyclic compounds. Many drugs, natural productsand synthetic materials contain pyrrole structural unit. In the past century, therefore, synthesisof pyrrole and its derivatives has been a research focus in organic synthesis. However, newand straightforward methods to access these compounds from simple starting materials arestill highly desirable, in particular the approach has the advantage of being amenable tostructural diversification.
In this thesis, we have developed novel and efficient domino reactions for the synthesisof polysubstituted pyrroles, fused pyrrole and indolizidine derivatives. These methods haveapparent advantages, such as readily available starting materials, mild reaction conditions,atom and step economy and diversification of product structure. Mechanisms of these newreactions are also investigated in details.
The thesis is divided into six chapters. In chapter one, the development of tandemreactions, heterocyclization based on methyl isocyanide and pyrrole synthesis in recent yearsare reviewed. The thesis proposal is presented in chapter two.
Chapter three describes an efficient and atom-economic strategy for the synthesis ofcyclopenta[b]pyrroles under extremely mild and transition metal-free conditions. In thetandem reaction, a new paradigm for trapping of the incipient imidoyl anion by intramolecularγ-carbon electrophile is realized, and two C–C sigma bonds are formed.
Chapter four shows a tandem Michael addition/isocyanide insertion reaction ofα,β-unsaturated ketone and tosyl methyl isocyanide. A concise and efficient methodology forthe one-pot synthesis of a variety of functionalized2-acylpyrroles is developed. For the fristtime, we have realized the isocyanide insertion into C–C bond reactions.
In chapter five, a synthetic method of indole-4,7-quinones, seven-andeight-membered-ring fused pyrroles from cyclic α,β-unsaturated ketone and tosyl methylisocyanide, which went through Michael addition/isocyanide insertion into acyl C–C bondprocess, is described. The initial carbon rings are expanded by one-carbon-atom while thepyrrole rings were constructed.
Chapter six, under catalysis of alkali, we have developed a new tandem [7+1]annulation/intramolecular cyclization reaction from the reaction of ethyl isocyanoacetate with-dialkenoyl ketene dithioacetals. This reaction features high to excellent yields, mildtransition metal-free conditions, high diastereoselectivity and perfect atom-economy.Furthermore, a series of8-azabicyclo[5.2.1]dec-8-enes and tricyclic indolizidine derivativeswith six adjacent stereocenters were synthesized in excellent yields in one-step.
本论文通过发展新颖、高效的多米诺反应，为多取代吡咯、并环吡咯及吲哚里西啶化合物提供新合成策略。所采用的方法具有原料易得、反应条件温和、产物结构多样化、反应步骤经济性高等优点。同时，对反应机理进行了深入细致的研究。
论文共分六个章节。第一章综述了多米诺反应、基于甲基异腈的杂环化反应及吡咯合成的研究进展。第二章提出了本论文的选题依据。
第三章研究了在温和条件下，无需过渡金属催化，高效，原子经济性地一步合成多取代环戊烷并吡咯化合物的新合成策略。该多米诺反应首次实现了分子内γ-位碳亲电体捕捉原位生成的亚胺负离子，成功地使异腈的端碳连续发生两次反应，构建了两个C–Cσ键。
第四章发展了α,β-不饱和酮和对甲苯磺酰基甲基异腈的串联Michael加成/异氰对C–C键插入反应，为多取代2-酰基吡咯化合物提供简洁、高效的合成方法。首次实现了分子内α-位碳亲电体捕捉原位生成的亚胺负离子。
第五章通过环状α,β-不饱和酮与对甲苯磺酰甲基异腈的串联Michael加成/异氰对C–C键插入反应，在构建吡咯环的同时通过C–C键插入形成苯并吲哚二酮及七/八元并环吡咯化合物。
第六章，在碱催化下，首次实现了通过非环状前体—-双烯酰基二硫缩烯酮与甲基异腈的新型串联[7+1]环加成/分子内环化反应，高产率、高非对映选择性、高原子经济性地构筑了氮杂八元双环化合物和含有六个相邻手性中心的吲哚里西啶衍生物，实现了在无过渡金属催化条件下的中环化合物的合成。
Pyrroles are an important class of heterocyclic compounds. Many drugs, natural productsand synthetic materials contain pyrrole structural unit. In the past century, therefore, synthesisof pyrrole and its derivatives has been a research focus in organic synthesis. However, newand straightforward methods to access these compounds from simple starting materials arestill highly desirable, in particular the approach has the advantage of being amenable tostructural diversification.
In this thesis, we have developed novel and efficient domino reactions for the synthesisof polysubstituted pyrroles, fused pyrrole and indolizidine derivatives. These methods haveapparent advantages, such as readily available starting materials, mild reaction conditions,atom and step economy and diversification of product structure. Mechanisms of these newreactions are also investigated in details.
The thesis is divided into six chapters. In chapter one, the development of tandemreactions, heterocyclization based on methyl isocyanide and pyrrole synthesis in recent yearsare reviewed. The thesis proposal is presented in chapter two.
Chapter three describes an efficient and atom-economic strategy for the synthesis ofcyclopenta[b]pyrroles under extremely mild and transition metal-free conditions. In thetandem reaction, a new paradigm for trapping of the incipient imidoyl anion by intramolecularγ-carbon electrophile is realized, and two C–C sigma bonds are formed.
Chapter four shows a tandem Michael addition/isocyanide insertion reaction ofα,β-unsaturated ketone and tosyl methyl isocyanide. A concise and efficient methodology forthe one-pot synthesis of a variety of functionalized2-acylpyrroles is developed. For the fristtime, we have realized the isocyanide insertion into C–C bond reactions.
In chapter five, a synthetic method of indole-4,7-quinones, seven-andeight-membered-ring fused pyrroles from cyclic α,β-unsaturated ketone and tosyl methylisocyanide, which went through Michael addition/isocyanide insertion into acyl C–C bondprocess, is described. The initial carbon rings are expanded by one-carbon-atom while thepyrrole rings were constructed.
Chapter six, under catalysis of alkali, we have developed a new tandem [7+1]annulation/intramolecular cyclization reaction from the reaction of ethyl isocyanoacetate with-dialkenoyl ketene dithioacetals. This reaction features high to excellent yields, mildtransition metal-free conditions, high diastereoselectivity and perfect atom-economy.Furthermore, a series of8-azabicyclo[5.2.1]dec-8-enes and tricyclic indolizidine derivativeswith six adjacent stereocenters were synthesized in excellent yields in one-step.
引文
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