<p> 异喹啉-1(2<em>H</em>)-酮及其衍生物作为重要的分子骨架广泛存在于天然产物、合成药物和生物活性分子中。这些化合物因独特的生物和药理活性而被应用于各个领域，因此备受研究者的关注。在过去几十年里，化学家们开发了多种方法来合成上述重要的分子砌块，但仍存在一些不足。比如：反应步骤较长、底物范围比较有限、反应条件比较苛刻、需要强酸或强碱和区域选择性较差等。异腈作为重要的合成原料，因其独特的化学性质常常用来合成各种酰胺类和杂环化合物，而这些化合物被进一步用于合成各种复杂的具有生物活性的药物和天然产物分子。因此，进一步开发反应条件温和且高效的合成异喹啉-1(2<em>H</em>)-酮的新方法和拓展异腈反应的多样性仍具有十分重要的意义。</p> <p> 苯炔作为一种活性中间体，被广泛应用于各种杂环芳香化合物的合成中。苯炔参与的反应具有反应条件温和，操作简单，底物普适性好等优点。在本论文中，苯炔分别与4, 5-二取代噁唑和异氰基酯进行反应，制备了异喹啉-1(2<em>H</em>)-酮和邻位含异氰基的苯甲酸甲酯。主要包括以下两部分内容：</p> <p> 1. 苯炔与4, 5-二取代噁唑经Diels-Alder反应、脱氢-芳构化、互变异构的串联反应，以中等至优异的产率得到了4-胺基异喹啉-1(2<em>H</em>)-酮。通过改变噁唑环上4、5位的取代基以及不同苯炔前体对反应进行了底物普适性研究，目标产物仍获得了较高的收率。为了进一步证明该反应的实用性，本实验还对该反应进行了克级规模放大反应、一锅法反应和各种衍生化反应研究。该方法突破了之前文献报道的苯炔与噁唑反应仅生成含氧桥环化合物的产物局限性，开发了一种无过渡金属参与的，反应条件温和的快速构建4-胺基异喹啉-1(2<em>H</em>)-酮及其衍生物的新方法。</p> <p> 2. 苯炔与异氰基酯经去质子化-亲核加成、分子内亲核环化-开环和再质子化过程最终生成邻位含异氰基的苯甲酸甲酯，该反应实现了苯炔对异氰基酯的C-C <em>&sigma;</em> 键插入反应。本实验在对反应条件进行了大量筛选后发现，苯甲酸甲酯衍生物的产率最高只能达到57%。作者在对反应副产物的分离过程中得到了主要的副产物是2-(3-氰基萘-2-基)-2-苯乙酸甲酯，分离收率在20-35%之间。随后作者通过核磁和单晶衍射对该副产物结构进行了确认并提出了主产物和副产物产生的可能反应机理。正是由于该副产物的竞争反应，导致该反应目标化合物产率一时难以提高。该研究结果为邻位含异氰基的苯甲酸甲酯提供了一种新的方法，同时也为异氰基酯与苯炔反应的多样化制备不同产物提供了一个新的思路。</p> <p> &nbsp;</p>

<p> Isoquinolin-1(2<em>H</em>)-ones and its derivatives as important building bilocks are widely found in natural products, synthetic drugs and biologically active molecules. These compounds have been used in various fields due to their unique biological and pharmacological activities, so they have attracted more attention form researchers. Over the past few decades, chemists have developed a variety of methods to synthesize aforementioned two important types of molecular skeletons, but there are still some drawbacks. For example, multi-step reaction; narrow substrate scope; harsh reaction conditions, requiring strong acid or strong base; poor regioselectivity, etc. Isonitriles as an important feedstock, because of its special reactivity, usually were used to synthesize various amides and heterocyclic compounds. These compounds were further treated to prepare some complex and biologically active drugs and natural products. Therefore, it is still of great significance to further develop more efficient new methods for the synthesis of isoquinolin-1(2<em>H</em>)-ones under mild reaction conditions and expand the reaction diversity of isonitriles.</p> <p> As active intermediates, benzynes have been widely used in the synthesis of various heterocyclic aromatic compounds. The reactions involving benzynes usually present following advantages: mild reaction conditions, simple operation and good substrates compatiblility. In this thesis, isoquinolin-1(2<em>H</em>)-ones and ortho-containing isocyano methyl benzoates were prepared by reacting benzynes with 4, 5-disubstituted oxazoles and isocyano esters, respectively. It mainly includes the following two parts:</p> <p> 1. The tandem reaction of benzynes and 4, 5-disubstituted oxazoles via Diels-Alder reaction, dehydrogenation-aromatization, and tautomerization afforded 4-aminoisoquinoline-1(2<em>H</em>)-ones. The substrate scopes of this reaction were studied by adjusting the substituents at 4- or 5-positions on the oxazole ring and different benzyne precusors, the target products were still obtained with high yields. In order to further prove the practicality of this methodology, the gram-scale reaction, one-pot reaction and many derivatization reactions were also carried out in this research. This method break through the limitation of previous reports about the reaction of benzyne and oxazole only affording oxygen-containing bridged ring compounds, and developed a transition-metal-free approach to rapidly construct 4-aminoisoquinoline-1(2<em>H</em>)-ones and its derivatives</p> <p> 2. The process for reacting benzynes with isocyano esters involving deprotonation-nucleophilic addition, intramolecular nucleophilic cyclization and ring opening, re-protonation, finally produces ortho-containing isocyano methyl benzoates. This reaction fulfilled the C-C <em>&sigma;</em> bond insertion between benzynes and isocyano esters. In this study, after various screening of the reaction conditions, the highest isolated yield of methyl benzoate compounds only could be 57% so far. The author obtained the main by-product methyl 2-(3-cyanonaphthalen-2-yl)-2-phenylacetate ester during the separation of the by-product in the reaction, and its isolate yield was generally within 20-35%. The structure of this by-product was clearly confirmed by NMR and X-ray analysis and the plausible recation mechanisms of main product and by-product were proposed by author.&nbsp; Due to the competitive reaction of the by-product, the yield of target product is enhanced difficultly. This discovery provides a new method for the synthesis of ortho-containing isocyano methyl benzoates and a new idea for the divergent preparation of different products by reacting isocyano esters with benzynes.</p> <p> &nbsp;</p>

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