本论文研究了银盐和手性三唑卡宾序列催化N'-(o-芳乙炔基亚苄基)磺酰肼与环丙基甲醛的反应。我们研究发现，在三氟乙酸银和手性茚并[2,1-b][1,2,4]三唑并[4,3-d][1,4]噁嗪盐产生的手性三唑卡宾序列催化下，N'-(o-芳乙炔基亚苄基)磺酰肼与环丙基甲醛反应以32%-82%的化学产率和优异的对映选择性 (99% - 99.9% ee) 和非对映选择性 (dr 11 : 1 - > 50 : 1) 生成顺式取代的亚胺键桥连苯并[c]氮杂?-3-酮化合物，同时反应也生成少量的多取代异喹啉衍生物，副产物产率在6-24%范围内。该反应经历了Ag (I) 催化N'-(o-芳乙炔基亚苄基)磺酰肼分子内环化形成N-酰胺基异喹啉叶立德，以及氮杂环卡宾催化环丙基甲醛与异喹啉偶极体之间的[3+2]环加成和1,3-N迁移反应。进一步研究表明，在DBU催化下，顺式取代的亚胺桥连苯并[c]氮杂?-3-酮主产物与其反式取代非对映体互相转变，因此，通过DBU催化顺式取代主产物异构化，我们以43-49%的产率得到了原反应中形成的微量反式取代异构体。此外，我们还将反应进行了克级实验，发现主产物的产率和对映选择性并没有明显降低，这也增加了反应的应用价值。最后，我们还研究了主产物的转化反应，将主产物通过氰基硼氢化钠还原亚胺键，以中等产率和优异的对映和非对映选择性得到仲胺桥连的苯并[c]氮杂?-3-酮 (58-62% yields, 99.4-99.6% ee, 20 : 1-31 : 1 dr)，从而进一步发展了复杂分子的多样性，拓展了该反应的应用范围。

本论文共合成了55个新化合物，所有的新化合物均通过IR、¹H NMR、¹³C NMR 和HRMS表征，主产物及其异构和还原产物还通过手性HPLC测定了ee 值。另外，亚胺桥连苯并[c]氮杂?-3-酮主产物和其非对映体、异喹啉衍生物副产物、以及仲胺桥连的苯并[c]氮杂?-3-酮等新化合物的结构经过X-ray 单晶衍射分析确定。

总之，本论文在温和反应条件下，通过简单的起始原料和绿色的催化剂高效构建了对映纯的桥连苯并[c]氮杂?-3-酮化合物。该研究进一步证明了氮杂环卡宾与过渡金属联合催化在有机合成中的应用价值。

In this thesis, the silver (I) salt and chiral triazole carbene sequentially catalyzed reaction of N'-(2-(arylethynyl)benzylidene)sulfonohydrazides with cyclopropanecarbaldehydes has been studied. It was found that, sequentially catalyzed by the silver trifluoroacetate and chiral indeno[2,1-b][1,2,4]triazolo[4,3-d][1,4]oxazin-2-ium, the reaction afforded imine-bridged benzo[c]azepin-3-ones in 32%-82% yields with excellent enantioselectivity (99%-99.9% ee) and diastereoselectivity (dr 11 : 1 - > 50 : 1). Meanwhile, isoquinoline derivatives were obtained as minor products in 6-24% yields. The reaction underwent an Ag-catalyzed intramolecular cyclization of N'-(2-(arylethynyl)benzylidene)sulfonohydrazides to form the N-amidoisoquinolinium ylide intermediates. Subsequently, the reaction underwent a formal [3+2] annulation reaction between N-amidoisoquinolinium ylides and enolate intermediates derived from cyclopropanecarbaldehydes and NHC catalyst followed by a 1,3-N shift. On the other hand, a base-catalyzed transformation between the cis-substituted benzo[c]azepin-3-one major products and its trans-substituted isomers was observed. Consequently, we obtained the trans-substituted isomers, which were formed as the tiny products in the reactions of N'-(2-(arylethynyl)benzylidene)sulfonohydrazides with cyclopropanecarbaldehydes, in 43-49% yield by a DBU-catalyzed isomerization of the cis-substituted major products. In addition, we also conducted a gram-level experiment on this reaction. It was found that the yield and enantioselectivity of major product did not decrease obviously. The gram-level experiment demonstrated the value of the application of this reaction in organic synthesis. Finally, we have studied the transformation of the major products. Reduction the C=N bonds of the major products by NaBH₃CN in MeOH/THF led to the formation of secondary amine-bridged benzo[c]azepin-3-ones in moderate yield with excellent enantioselectivity and diastereoselectivity (58-62% yields, 99.4-99.6% ee and 20:1-31:1 dr). The transformation of products further developed the diversity of complex molecules and expanded the scope of application of this reaction.

In this thesis, a total of 55 new compounds were synthesized. All of the new compounds were characterized by IR, HRMS, ¹H NMR and ¹³C NMR. The ee values of the main products, the trans-isomers and the reduction products were determined by chiral HPLC. Among them, the structures of cis-substituted imine-bridged benzo[c]azepin-3-one major product, its trans-isomer, isoquinoline minor product and secondary amine-bridged benzo[c]azepin-3-one were confirmed by X-ray single crystal diffraction analysis.

In summary, we have developed a novel method for efficient construction optically pure nitrogen bridged benzo[c]azepin-3-ones through the cheap and easily available starting materials, green catalysts and mild conditions. This study demonstrated the application of the combination of N-heterocyclic carbene and transition metal catalysts in organic synthesis.