基于Isosteviol的新型有机催化剂的设计合成及不对称催化性能研究
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摘要
手性有机小分子催化是继有机金属催化和酶催化之后的又一种重要的不对称催化方法，近年来在新催化剂的设计和新催化概念的提出方面取得了很大的进展，并逐渐发展成为当代有机合成中最具活力的领域之一。其中基于“单分子、双功能活化”概念发展起来的各种手性骨架桥连的双功能胺-硫脲和胺-方酰胺类催化剂在一系列不对称催化反应中得到了广泛的应用，表现出了优秀的催化性能。本论文基于这一有机不对称催化新理念，从廉价易得且具有手性疏水骨架的天然异斯特维醇出发，在新型两亲双功能手性催化剂的设计合成及其在不对称C-C键形成反应中的应用方面开展了如下研究：
第一部分，简要介绍了手性的概念、不对称合成的意义，以及不对称有机催化；重点综述了双功能的手性胺-硫脲和手性胺-方酰胺两类催化剂在不对称Michael加成反应中的研究进展。
第二部分，基于双功能活化的理念和异斯特维醇的优秀手性骨架，设计合成了手性胺-硫脲型和手性胺-方酰胺型两类17个结构新颖的双功能有机小分子催化剂。经IR, NMR, HRMS及晶体结构测定表征确定了新化合物的结构和绝对构型。
第三部分，对设计合成的一系列双功能手性伯胺-硫脲催化剂在不对称Michael加成反应中的催化性能进行了考察，发现这类催化剂表现出了优良的催化活性和选择性的可控性。发展了双手性控制的异丁醛和硝基烯烃以及异丁醛和Ｎ-取代马来酰亚胺的不对称加成体系。在同一催化体系下，无论用哪种特定构型的催化剂，都可几乎立体选择性的得到一种手性加成产物，获得了优异的收率（up to98%）和对映选择性（up to99%ee）；此外，手性伯胺-硫脲型催化剂在水相和有机相中均能高效、高立体选择性的催化异丁醛与硝基烯烃的不对称加成反应；结合计算机模拟和理论计算，提出了催化反应的可能过渡态模型和机理。异丁醛与Ｎ-取代马来酰亚胺的不对称加成反应，放大量进行时，对收率和对映选择性均无影响。
第四部分，研究了新型手性叔胺-硫脲催化剂在乙酰丙酮与硝基烯烃的加成，以及α-芳基氰乙酸酯与N-取代马来酰亚胺的加成这两个体系中的应用。在乙酰丙酮和硝基烯烃的不对称加成中，两种不同构型的手性叔胺-硫脲型催化剂均表现出了优异的催化活性和立体选择性（up to95%yield, up to97%ee），且具有水平相当的双手性控制性能。在α-芳基氰乙酸酯与N-取代马来酰亚胺的不对称加成反应中，从(S,S)-构型的环己二胺出发合成的叔胺-硫脲催化性能更好（up to97%yield,98/2dr,93%ee）。
第五部分，首次报道了基于异斯特维醇的新型手性伯胺-方酰胺类有机催化剂的设计合成及在双手性控制的不对称C-C形成反应中的成功应用。发展了高效、高选择性的异丁醛与硝基烯烃、以及醛与Ｎ-取代马来酰亚胺的不对称Michael加成体系，以优异的收率（up to98%）和立体选择性（up to>99%ee）得到了相应的加成产物。
第六部分，研究了新型手性叔胺-方酰胺类催化剂在乙酰丙酮与硝基烯烃的Michael加成反应中的不对称催化性能。无论在无溶剂条件下或在有机溶剂中，这类手性叔胺-方酰胺型催化剂同样表现出了优异的催化效能，均能高效（无溶剂：up to95%；氯仿：up to97%）、高立体选择性（无溶剂：up to97%ee；氯仿：up to99%ee）的催化该反应。
Organocatalysis is the third important asymmetric catalytic method followingorganometallic catalysis and enzyme catalysis. Over the past decade, the research ofthis area has grown rapidly to become one of the most exciting current fields inorganic chemistry and much interest has been devoted to the development of highlyefficient organocatalysts for a variety of reactions. Since the "single molecule, dualactivation" concept was developed, a number of thiourea-based andsquaramide-based organocatalysts have been designed and widely applied in variousstereoselective transformations and exhibited excellent asymmetric catalyticactivities. Base on the new concept of organic asymmetric catalysis “bifunctionalorganocatalyst” and isostiviol, an inexpensive and readily available natural productpossessing a hydrophobic skeleton, design and synthesis of novel organocatalystsand their catalytic activities in asymmetric C-C bond forming reactions wereinvestigated.
In the first part of the dissertation, the concept of chirality, the meaning ofasymmetric synthesis, as well as asymmetric organocatalysis were briefly introduced.The recent progress on chiral amine-thiourea and amine-squaramide catalyzedstereoselective Michael addition has also been summarized.
In the second part, based on the “bifunctional catalyst” concept, two novel kinds ofchiral thiourea and squaramide organocatalysts were designed and synthesizedstarting from isosteviol and DACH.
In the third part of the thesis, highly doubly stereocontrolled enantioselectiveMichael addition of isobutyraldehyde to nitroalkenes and aldehyde to N-substitutedmaleimides were developed by using the chiral amine-thiourea catalysts.Furthermore, the reactions of isobutyraldehyde and nitroalkenes proceeded smoothlyboth in organic solvents and in water under mild conditions. High isolated yields (upto98%) and enantioselectivities (up to99%ee) were obtained using our catalyticsystem. In addition, combined with the computer simulation and theoretical calculation, the proposed reaction mechanism and working model of transition statewere suggested. Furthermore, the catalytic system of aldehyde and N-substitutedmaleimides can be used efficiently in large-scale reactions with the yields andenantioselectivities being maintained at the same level.
In the following study, we described two highly efficient oaganocatalyticasymmetric Michael additions of acetylacetone to nitroolefins and α-substitutedcyanoacetates to maleimides promoted by novel isosteviol-derived bifunctionalthiourea. Doubly stereocontrolled organosyntheses were achieved in the Michaeladdition of acetylacetone and nitroolefins, comparable isolated yields (up to95%)and enantioselectivities (up to97%ee) were obtained. While in the reaction ofα-substituted cyanoacetates and maleimides, thiourea the catalysts obtained from(S,S)-DACH showed better asymmetric catalytic activities.
In the next part, we reported, for the first time, the asymmetric catalytic behaviorsof the novel chiral bifunctional primary amine-squaramide organocatalysts based onisostiviol. Their successful applications in the doubly stereocontrolledenantioselective Michael addition of isobutyraldehyde to nitroalkenes (up to98%yield and up to99%ee) as well as the aldehyde to N-substituted maleimides (up to98%yield and up to99%ee) were described. The possible reaction mechanism andtransition state were also proposed.
In the six part of the dissertation, we presented the highly enantioselectiveMichael addition of acetylacetone to nitroolefins catalyzed by the novelisosteviol-based thiral amine-squaramide organocatalyst. It is worth mentioning thatthe reactions carried out smoothly both in neat conditions and in CHCl3, and bothgave high isolated yields (up to95%in neat condition; up to97%in CHCl3) andenantioselectivities (up to97%in neat condition; up to99%in CHCl3).
第一部分，简要介绍了手性的概念、不对称合成的意义，以及不对称有机催化；重点综述了双功能的手性胺-硫脲和手性胺-方酰胺两类催化剂在不对称Michael加成反应中的研究进展。
第二部分，基于双功能活化的理念和异斯特维醇的优秀手性骨架，设计合成了手性胺-硫脲型和手性胺-方酰胺型两类17个结构新颖的双功能有机小分子催化剂。经IR, NMR, HRMS及晶体结构测定表征确定了新化合物的结构和绝对构型。
第三部分，对设计合成的一系列双功能手性伯胺-硫脲催化剂在不对称Michael加成反应中的催化性能进行了考察，发现这类催化剂表现出了优良的催化活性和选择性的可控性。发展了双手性控制的异丁醛和硝基烯烃以及异丁醛和Ｎ-取代马来酰亚胺的不对称加成体系。在同一催化体系下，无论用哪种特定构型的催化剂，都可几乎立体选择性的得到一种手性加成产物，获得了优异的收率（up to98%）和对映选择性（up to99%ee）；此外，手性伯胺-硫脲型催化剂在水相和有机相中均能高效、高立体选择性的催化异丁醛与硝基烯烃的不对称加成反应；结合计算机模拟和理论计算，提出了催化反应的可能过渡态模型和机理。异丁醛与Ｎ-取代马来酰亚胺的不对称加成反应，放大量进行时，对收率和对映选择性均无影响。
第四部分，研究了新型手性叔胺-硫脲催化剂在乙酰丙酮与硝基烯烃的加成，以及α-芳基氰乙酸酯与N-取代马来酰亚胺的加成这两个体系中的应用。在乙酰丙酮和硝基烯烃的不对称加成中，两种不同构型的手性叔胺-硫脲型催化剂均表现出了优异的催化活性和立体选择性（up to95%yield, up to97%ee），且具有水平相当的双手性控制性能。在α-芳基氰乙酸酯与N-取代马来酰亚胺的不对称加成反应中，从(S,S)-构型的环己二胺出发合成的叔胺-硫脲催化性能更好（up to97%yield,98/2dr,93%ee）。
第五部分，首次报道了基于异斯特维醇的新型手性伯胺-方酰胺类有机催化剂的设计合成及在双手性控制的不对称C-C形成反应中的成功应用。发展了高效、高选择性的异丁醛与硝基烯烃、以及醛与Ｎ-取代马来酰亚胺的不对称Michael加成体系，以优异的收率（up to98%）和立体选择性（up to>99%ee）得到了相应的加成产物。
第六部分，研究了新型手性叔胺-方酰胺类催化剂在乙酰丙酮与硝基烯烃的Michael加成反应中的不对称催化性能。无论在无溶剂条件下或在有机溶剂中，这类手性叔胺-方酰胺型催化剂同样表现出了优异的催化效能，均能高效（无溶剂：up to95%；氯仿：up to97%）、高立体选择性（无溶剂：up to97%ee；氯仿：up to99%ee）的催化该反应。
Organocatalysis is the third important asymmetric catalytic method followingorganometallic catalysis and enzyme catalysis. Over the past decade, the research ofthis area has grown rapidly to become one of the most exciting current fields inorganic chemistry and much interest has been devoted to the development of highlyefficient organocatalysts for a variety of reactions. Since the "single molecule, dualactivation" concept was developed, a number of thiourea-based andsquaramide-based organocatalysts have been designed and widely applied in variousstereoselective transformations and exhibited excellent asymmetric catalyticactivities. Base on the new concept of organic asymmetric catalysis “bifunctionalorganocatalyst” and isostiviol, an inexpensive and readily available natural productpossessing a hydrophobic skeleton, design and synthesis of novel organocatalystsand their catalytic activities in asymmetric C-C bond forming reactions wereinvestigated.
In the first part of the dissertation, the concept of chirality, the meaning ofasymmetric synthesis, as well as asymmetric organocatalysis were briefly introduced.The recent progress on chiral amine-thiourea and amine-squaramide catalyzedstereoselective Michael addition has also been summarized.
In the second part, based on the “bifunctional catalyst” concept, two novel kinds ofchiral thiourea and squaramide organocatalysts were designed and synthesizedstarting from isosteviol and DACH.
In the third part of the thesis, highly doubly stereocontrolled enantioselectiveMichael addition of isobutyraldehyde to nitroalkenes and aldehyde to N-substitutedmaleimides were developed by using the chiral amine-thiourea catalysts.Furthermore, the reactions of isobutyraldehyde and nitroalkenes proceeded smoothlyboth in organic solvents and in water under mild conditions. High isolated yields (upto98%) and enantioselectivities (up to99%ee) were obtained using our catalyticsystem. In addition, combined with the computer simulation and theoretical calculation, the proposed reaction mechanism and working model of transition statewere suggested. Furthermore, the catalytic system of aldehyde and N-substitutedmaleimides can be used efficiently in large-scale reactions with the yields andenantioselectivities being maintained at the same level.
In the following study, we described two highly efficient oaganocatalyticasymmetric Michael additions of acetylacetone to nitroolefins and α-substitutedcyanoacetates to maleimides promoted by novel isosteviol-derived bifunctionalthiourea. Doubly stereocontrolled organosyntheses were achieved in the Michaeladdition of acetylacetone and nitroolefins, comparable isolated yields (up to95%)and enantioselectivities (up to97%ee) were obtained. While in the reaction ofα-substituted cyanoacetates and maleimides, thiourea the catalysts obtained from(S,S)-DACH showed better asymmetric catalytic activities.
In the next part, we reported, for the first time, the asymmetric catalytic behaviorsof the novel chiral bifunctional primary amine-squaramide organocatalysts based onisostiviol. Their successful applications in the doubly stereocontrolledenantioselective Michael addition of isobutyraldehyde to nitroalkenes (up to98%yield and up to99%ee) as well as the aldehyde to N-substituted maleimides (up to98%yield and up to99%ee) were described. The possible reaction mechanism andtransition state were also proposed.
In the six part of the dissertation, we presented the highly enantioselectiveMichael addition of acetylacetone to nitroolefins catalyzed by the novelisosteviol-based thiral amine-squaramide organocatalyst. It is worth mentioning thatthe reactions carried out smoothly both in neat conditions and in CHCl3, and bothgave high isolated yields (up to95%in neat condition; up to97%in CHCl3) andenantioselectivities (up to97%in neat condition; up to99%in CHCl3).
引文
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