【作者】 王莉莉；

【导师】 朱进；

【作者基本信息】 南京大学 ， 化学工程（专业学位）， 2018， 硕士

【摘要】 在有机和药物化学分子的合成中,以过渡金属为催化剂的C-H活化反应已经日渐成熟。由于C-H功能化的步骤经济和原子经济型,该过程可以大大简化药物、天然产物、农用化学品、聚合物和原料化学品的合成。本文主要研究了钴和铑催化的C-H键官能化在杂环化合物合成方面的应用。主要内容包括:1.介绍了钴催化的C-H键活化构建杂环化合物的发展现状。简单的介绍了 Cp*Co(Ⅲ)和廉价Co催化体系双齿配位的研究进展,按照烯烃化,炔烃化,芳基化,烯丙基化,羰基化,氰基化等分类,对过渡金属催化C-H活化经行了简要的分类。2.廉价Co(Ⅱ)催化氧化C-H活化环化反应本章节主要研究了 Co(Ⅱ)催化的双齿配位的C-H活化环化合成异喹啉。Co(Ⅱ)催化的2-吡啶肼为导向基的C-H活化环化合成异喹啉。通过C-H活化合成异喹啉结构的方法有很多,但是本文首次使用廉价钴催化双齿配位合成该化合物,因此该导向基团在双齿配位C-H活化领域中具有一定的推动意义。该反应具有以下优点:1)首次使用该导向基进行C-H活化;2)2-吡啶基能在环化后脱去;3)以空气中的氧气作为氧化剂。此外,研究了该反应体系的机理,结果表明C-H活化步骤在催化过程中可能是决速步。3.Cp*Rh(Ⅲ)催化C-H活化环化反应本章节主要研究了 N-叔丁基羰基酯(N-Boc)键断裂在C-H键活化反应中构建氮杂环化合物。在Rh(Ⅲ)催化体系中,N-Boc苯乙酮腙与重氮双酯偶联生成了苯并二氮卓类物质,该物质是一种重要的含氮杂环骨架,在药物化学中具有许多重要的药理和生物学活性。例如,托非索洋镇静剂,奈立索泮和吉立索泮等具有生物活性的药物,分子中都包含苯并[2,3]二氮卓结构。更多还原

【Abstract】 In the synthesis of organic and medicinal molecules,the C-H activation with the transition metal-catalyst has been increasingly mature.Because of the steps economic and atomic economic,C-H functionalization processes can significantly simplify the synthesis of pharmaceuticals,natural products,agrochemicals,polymers,and feedstock commodity chemicals.In this paper,we studied the application of C-H bond functionalization to synthesis of heterocyclic structures via cobalt and rhodium catalyst.The main contents include:1.Introduced the development status of heterocyclic compounds synthesised by C-H activation of cobalt catalysis.Simple introduced the Cp*Co(Ⅲ)and the cheap cobalt catalyst,the research progress is classificated according to alkenes,alkynes,aromatic,allylation,carbonylation and cyano.2.Cheap Co(Ⅱ)catalytic oxidation C-H activation cyclization.In this chapter,we report a traceless Cobalt-catalyzed bidentate C-H activation approach for in-situ synthesis of isoquinoline.There have a lot of methods to synthesis isoquinoline structure via C-H activation,but it was the first time which used cheap cobalt catalyst bidentate C-H activation,so it has a certain meaning in the field of C-H activation.The reaction has the following advantages:1)The first time to used that directing group.2)2-pyridine can be removed after cyclization.3)Use oxygen in the air as an oxidant.Furthermore,the mechanism of this reaction system was examined and the result shown that the C-H activation step was rate-determining in the catalytic process.3.Cp*Rh(Ⅲ)catalyzes C-H activation cyclization.In this chapter,we report the discovery of N-tert-butyloxycarbonyl(N-Boc)cleavage to construct the nitrogen heterocyclic compound.Rh(Ⅲ)-catalyzed coupling of N-Boc hydrazone with diazodiester provides efficient access to produced 2,3-Benzodiazepines,an important structural motif present in drug compounds,which can exhibit many important pharmacological and biological activities.For example,tofisopam is an anxiolytic agent in humans,nerisopam and girisopam proved to be biologically active.更多还原