| 钴催化脂肪酰胺C(sp3)-H键的氧化羰基化反应 |
| Alternative Title | Cobalt-Catalyzed Oxidative C(sp3)-H Carbonylation of Aliphatic Amides
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| 王丹 |
| Subtype | 学士
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| Thesis Advisor | 刘珍伶
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| 2016-05-21
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| Degree Grantor | 兰州大学
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| Place of Conferral | 兰州
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| Degree Name | 学士
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| Keyword | 钴催化
C(sp3)-H键
氧化羰基化
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| Abstract | 过渡金属催化的有机合成反应是当下化学研究的热门领域，其中过渡金属催化的羰基化反应更是成为构建羰基化合物的重要方法之一，过去的几十年间过渡金属催化有机卤代物的羰基化反应经历了快速的发展。然而有机卤代物通常由相似的烃类制得，这便不符合原子经济性的理念。作为一个选择，C-H 键氧化羰基化在过去的几年间引起了广泛的关注。根据亲核试剂的不同，该类型反应可以生成不同的羰基衍生物，如酸，酯，酰胺以及酮等。近年来芳基C(sp2)-H的氧化羰基化的得到了广泛的研究，而对于更为广泛存在的C(sp3)-H的研究较少，同时目前氧化羰基化反应的研究大多需要使用贵金属铑、钌、钯等作为催化剂。
不活泼的C(sp3)-H键的活化对于自然科学非常重要，其中C(sp3)-H键的氧化羰基化是其中的一个重要的分支。我们利用较为廉价易得的钴盐作为催化剂，以碳酸银作为氧化剂，以碱作为脱氢试剂，以一氧化碳作为羰基源，同时活化不活泼的C(sp3)-H键和一氧化碳小分子，实现烷基酰胺的C(sp3)-H键的氧化羰基化反应。
本文一定程度上创新了原有的C(sp3)-H键的氧化羰基化反应的方法，是一种十分有效的直接利用烷基酰胺中不活泼的C(sp3)-H和一氧化碳合成杂环的方式，在有机合成中有潜在的应用价值。 |
| Other Abstract | Organic synthesis via transition-metal catalysis has been the frontier area of the whole chemistry research. As a branch, the transition-metal-catalyzed carbonylation which is one of the most significant methods to construct the carbonyl compounds has attracted more and more attention. Transition-metal-catalyzed carbonylation reactions of organic halides have undergone a rapid development. However, most of the organic halides come from the corresponding hydrocarbon, which do not conform to the concept of atom economy. As one of the choices, the oxidative C-H carbonylation has aroused a broad attention. Based on the types of the nucleophiles, a variety of carbonyl compounds like acids, esters, amides and ketones can be synthesized via the oxidative carbonylation reactions. In recent years, the aromatic C (sp2) - H oxidation carbonylation got extensive research, and for a more widespread C (sp3) - H study is less, meanwhile oxidative carbonylation reaction of most studies are required to use precious metal rhodium, ruthenium, palladium as a catalyst, etc.
Inert C (sp3) - H bond activation is important for natural science, in which C (sp3) - H bond oxidative carbonylation is one of the important branch. Have reported some cobalt catalyst activation before C (sp3) - H bond articles, but is generally and another kind of compounds containing active H reaction, implement C (sp3) - H bond cross-coupling reaction. We use cheap easy cobalt salt as a catalyst, silver carbonate as oxidant, with alkali reagent as dehydrogenation, carbon monoxide as source of carbonyl group, at the same time activation of inert C(sp3) - H bond and small molecules carbon monoxide, realization of alkyl amide C(sp3) - H bond oxidative carbonylation reaction.
In this paper, the innovation of the original C (sp3) - H bond oxidative carbonylation reaction, that is a kind of very effective synthetic method direct use of inert alkyl amide C(sp3) - H and carbon monoxide to heterocyclic, has potential application value in organic synthesis. |
| URL | 查看原文
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| Language | 中文
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| Document Type | 学位论文
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| Identifier | https://ir.lzu.edu.cn/handle/262010/237734
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| Collection | 化学化工学院
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Recommended Citation
GB/T 7714 |
王丹. 钴催化脂肪酰胺C(sp3)-H键的氧化羰基化反应[D]. 兰州. 兰州大学,2016.
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