N-杂环卡宾催化下δ-内酰胺、螺吲哚四氢吡喃-2-酮及萘并二氢吡喃酮的串联合成
发布时间：2018-10-16 09:47
【摘要】：N-杂环卡宾作为化学反应的催化剂,在有机催化反应中扮演着重要的角色,它们不仅可以作为亲核试剂参与反应,也可以作为路易斯碱和布朗斯特碱参与有机催化反应。目前,N-杂环卡宾催化剂仍然是有机催化反应中的研究热点之一。N-杂环卡宾催化剂手性骨架的引入,可以很方便地不对称合成不同骨架的化合物。本论文主要围绕N-杂环卡宾催化下δ-内酰胺骨架、螺吲哚四氢吡喃-2-酮骨架及萘并二氢吡喃酮骨架的串联合成等课题进行展开。研究工作包括以下四个部分。第一部分:介绍了N-杂环卡宾的发现、结构的确认、参与催化反应的性质和类型,以及近年来N-杂环卡宾的发展历史。最后介绍了该论文的创新点。第二部分:介绍了手性卡宾催化酰腙与α-溴代-α,β-不饱和醛的反应,不对称地合成δ-内酰胺骨架衍生物。这种方法具有高产率、高对映选择性、原料易得、反应条件温和等特点。第三部分:介绍N-杂环卡宾催化溴代烯醛与氧化吲哚非对映选择性构建螺吲哚四氢吡喃-2-酮骨架。这种方法具有原料易得、非对映选择性高、产率较好等优点。进一步发展了螺吲哚四氢吡喃-2-酮的合成途径。第四部分:介绍N-杂环卡宾催化溴代烯醛与β-四氢萘满酮来不对称构建萘并二氢吡喃酮骨架。这种方法具有简便易得的原料、产率很好和对映选择性很高等优点。
[Abstract]:N- heterocyclic carbene, as a catalyst for chemical reaction, plays an important role in organic catalytic reactions. They can be used not only as nucleophilic reagents, but also as Lewis base and Brownst base to participate in organic catalytic reactions. At present, N-heterocyclic carbene catalyst is still one of the hot spots in organic catalytic reaction. The introduction of chiral skeleton of N-heterocyclic carbene catalyst can facilitate asymmetric synthesis of compounds with different skeletons. This thesis focuses on the series synthesis of 未-lactam framework, spiroindole tetrahydropyrane-2-one skeleton and naphthalene dihydropyranone skeleton catalyzed by N-heterocyclic carbene. The research includes the following four parts. The first part introduces the discovery of N-heterocyclic carbene, the confirmation of structure, the nature and type of catalytic reaction, and the development history of N-heterocyclic carbene in recent years. Finally, the innovation of this paper is introduced. The second part: chiral carbene catalyzed the reaction of acylhydrazone with 伪-bromo- 伪, 尾-unsaturated aldehydes and asymmetric synthesis of 未-lactam skeleton derivatives. This method is characterized by high yield, high enantioselectivity, easy availability of raw materials and mild reaction conditions. Part three: N-heterocyclic carbene catalyzed the enantioselectivity of brominoalkenal and oxindole to construct spiroindole tetrahydropyran-2-one skeleton. This method has the advantages of easy preparation of raw materials, high enantioselectivity and good yield. The synthesis of spiroindole tetrahydropyran-2-one was further developed. Part four: N-heterocyclic carbene catalyzed the asymmetric construction of naphthalene dihydropyranone framework with brominated aldehydes and 尾 -tetrahydronaphthalenone. This method has the advantages of simple and easy to obtain raw materials, good yield and high enantioselectivity.
【学位授予单位】：江苏师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
[Abstract]:N- heterocyclic carbene, as a catalyst for chemical reaction, plays an important role in organic catalytic reactions. They can be used not only as nucleophilic reagents, but also as Lewis base and Brownst base to participate in organic catalytic reactions. At present, N-heterocyclic carbene catalyst is still one of the hot spots in organic catalytic reaction. The introduction of chiral skeleton of N-heterocyclic carbene catalyst can facilitate asymmetric synthesis of compounds with different skeletons. This thesis focuses on the series synthesis of 未-lactam framework, spiroindole tetrahydropyrane-2-one skeleton and naphthalene dihydropyranone skeleton catalyzed by N-heterocyclic carbene. The research includes the following four parts. The first part introduces the discovery of N-heterocyclic carbene, the confirmation of structure, the nature and type of catalytic reaction, and the development history of N-heterocyclic carbene in recent years. Finally, the innovation of this paper is introduced. The second part: chiral carbene catalyzed the reaction of acylhydrazone with 伪-bromo- 伪, 尾-unsaturated aldehydes and asymmetric synthesis of 未-lactam skeleton derivatives. This method is characterized by high yield, high enantioselectivity, easy availability of raw materials and mild reaction conditions. Part three: N-heterocyclic carbene catalyzed the enantioselectivity of brominoalkenal and oxindole to construct spiroindole tetrahydropyran-2-one skeleton. This method has the advantages of easy preparation of raw materials, high enantioselectivity and good yield. The synthesis of spiroindole tetrahydropyran-2-one was further developed. Part four: N-heterocyclic carbene catalyzed the asymmetric construction of naphthalene dihydropyranone framework with brominated aldehydes and 尾 -tetrahydronaphthalenone. This method has the advantages of simple and easy to obtain raw materials, good yield and high enantioselectivity.
【学位授予单位】：江苏师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
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