壹、 鈷金屬催化2-鹵苯甲醯胺與炔類偶合反應之研究 貳、 以鈷金屬催化2-溴苯甲醯胺與碳二亞胺環化合成3-亞胺基 異二氫吲哚-1-酮之研究 參、 以苯并噻三嗪之脫氮反應合成七元環磺內醯胺之研究

I. Cobalt-Catalyzed Coupling reactions of 2-halobenzamides with Alkynes. II. Cobalt-Catalyzed Cyclization of 2-Bromobenzamides with Carbodiimides: A New Route for the Synthesis of 3-(Imino)isoindolin-1-ones. III. Denitrogenative cyclization of benzothiatriazines to seven-membered sultams.

莊何曼(Hasil Aman)

指導教授 ： 莊 敬

中原大學/理學院/化學研究所/博士(2021年)

https://doi.org/10.6840/cycu202101029

摘要

本論文分為以下三部分：
壹、 鈷金屬催化2-鹵苯甲醯胺與炔類偶合反應之研究
貳、 以鈷金屬催化2-溴苯甲醯胺與碳二亞胺環化合成3-亞胺基異
二氫吲哚-1-酮之研究
參、 以苯并噻三嗪之脫氮反應合成七元環磺內醯胺之研究

　　第一章主題為以鈷金屬催化2-鹵化苯醯胺與炔類進行偶和反應進而合成異喹啉酮類型化合物的合成研究，內含反應機構的探討，此方法學也於合作實驗室用於nitidine類天然物的全合成。
　 第二章的研究則是探討同樣以鈷金屬類型催化劑，催化2-鹵化苯醯胺與碳二亞胺進行合環反應，用於合成3-亞胺基異吲哚酮類化合物。本合成方法之官能基相容性與產率皆屬優異。而我們對於此反應則是提出了一個經過含鈷金屬之五員雜環的反應機構。
　　第三章的內容則討論以苯並硫三嗪類型起始物進行脫氮反應，在分子內合環反應下得到七員環磺內醯胺此一特殊結構的研究。此新穎的反應無需催化劑與其他試劑的使用，並可用於合成具有生物活性之磺內醯胺化合物。

關鍵字

3-亞胺基 異二氫吲哚-1-酮 ； 碳二亞胺 ； 鈷金屬催化 ； 2-溴苯甲醯胺 ； 脫氮反應 ； 七元環磺內醯胺

並列摘要

The works presented are listed below:
• Cobalt-catalyzed coupling reactions of 2-halobenzamides with alkynes: investigation of ligand-controlled dual pathways.
• Cobalt-catalyzed coupling reactions of 2-halobenzamides with Carbodiimides: A Method to synthesize 3-iminoisoindolin-1-one
• Denitrogenative Tendem cyclization of benzothiatriazines to seven membered sultams.
First project has set out to design a cobalt-catalyzed coupling reactions of 2-halobenzamides with alkynes giving access to isoquinolinones. A mechanistic study has been performed to propose a suitable mechanism. Despite, the utility of this synthetic strategy was successfully tested for the synthesis of natural product nitidine and nitidine chloride.
The second project was dedicated to revealed a cobalt-catalyzed coupling reactions of 2-halobenzamides with carbodiimides which provides an alternate synthetic method for biologically important 3-iminoisoindolin-1-one. This catalytic reaction can tolerate a variety of substituents and provide the corresponding products in moderate yields for most cases. According to experimental evidences and literature, the reaction mechanism is proposed through the formation of a five-membered aza-cobalacycle complex.
Third, seven membered sultams were first time reported via denitrogenative coupling of 1,2,3,4-benzothitriazine. Product was obtained only by thermal activation without adding any catalyst or oxidant. The synthetic strategy was utilized to synthesized a biologically active sultam.

並列關鍵字

isoquinolinone ； carbodiimide ； cobalt-catalyzed ； C-C coupling reactions ； Denitrogenative cyclization ； seven membered-sultams

參考文獻

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