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| 研究生： |
張彧喆 Chang, Yu-Che |
|---|---|
| 論文名稱： |
錸金屬催化含氮雜環之碳－氫鍵烷基化及烯基化反應 Rhenium(I)-Catalyzed Direct C-H Alkylation and Alkenylation of Nitrogen Containing Heterocycles |
| 指導教授： |
鄭建鴻
Cheng, Chien-Hong |
| 口試委員: |
蔡易州
Tsai, Yi-Chou 謝仁傑 Hsieh, Jen-Chieh |
| 學位類別： |
碩士 Master |
| 系所名稱： |
理學院 - 化學系 Department of Chemistry |
| 論文出版年： | 2019 |
| 畢業學年度： | 107 |
| 語文別： | 中文 |
| 論文頁數： | 231 |
| 中文關鍵詞： | 錸金屬催化 、碳－氫鍵活化 、烷基化反應 、烯基化反應 |
| 外文關鍵詞： | Rhenium(I)-Catalyzed, C-H activation, Alkylation, Alkenylation |
| 相關次數： | 點閱：3 下載：0 |
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碳－碳多重鍵的合成在有機化學中一直是非常重要且熱門的研究方向。近年來，過渡金屬催化碳－氫鍵活化反應的發展在該領域更為有效率且符合原子經濟(atom economy)。雖然3d與4d過渡金屬如鈷、鐵、鎳、銠、釕、鈀等已被廣泛研究，但5d過渡金屬如銥、錸等卻顯為開發。因此，本論文主要探討以錸金屬作為催化劑活化含氮雜環化合物之碳－氫鍵與烯類、炔類化合物合成烷基化(alkylation)與烯基化(alkenylation)產物。此合成方法藉由微調反應溫度與時間的情況下，便可有效合成烷基化與烯基化產物，並具有非常優異的立體選擇性。在過去未有任何過渡金屬達成此成果。另外，本研究也針對錸金屬催化碳—氫鍵活化反應之反應機構進行研究，以電噴灑游離質譜技術(ESI-MS，electrospray ionization mass spectroscopy)偵測錸金屬碳—氫鍵活化五元環中間體(rhenium metallacycle)。
Hydroarylation of carbon-carbon multiple bonds via transition metal-catalyzed directed C¬¬-H bond activation provides the alkenylated and alkylated heterocycles with a higher atom economy. Notably, this protocol has been considered to be an important strategy to synthesize functionalized heterocycles. Hydroarylation reactions have been studied well with several 3d- and 4d-transition metals; However, the reactivity of 5d-transition metals, particularly, rhenium has been rarely discussed in this regard. Herein, we report a catalytic reactivity of Re(I) complexes for the hydroarylation reactions of bicyclic alkenes, terminal and internal alkynes via directed C-H bond activation strategy. This reaction features a very simple reaction condition, including relatively low amount of catalyst, short reaction time, broad substrates scope, and excellent selectivity. Moreover, the proposed mechanism is strongly supported by the detection of a five-membered rhenacycle intermediate by ESI-MS.
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