α-亞胺銠卡賓與醇、1,3-二羰基化合物的反應研究
發(fā)布時間：2019-04-22 12:44
【摘要】：金屬卡賓作為一類非常重要的有機合成中間體在有機化學中有著重要地位。近年來,N-磺�；�-1,2,3-三氮唑作為一種化學高效、安全、環(huán)境友好α-亞胺卡賓前體受到人們廣泛關注。其在以銠為主的金屬催化劑的作用下產生的α-亞胺金屬卡賓體可以通過環(huán)丙烷化反應、C-H、O-H以及N-H等插入反應以及其他類型卡賓參與的反應來構建一系列含氮骨架化合物。我們課題組通過N-磺�；�-1,2,3-三氮唑已經成功構建了吡咯及吡嗪骨架。在我們課題組此前工作基礎上發(fā)展了一種銠催化N-磺�；�-1,2,3-三氮唑與芐醇經歷O-H插入,[1,3]重排合成α-氨基酮化合物,并通過Pictet-Spengler反應進一步構建了多取代二氫異喹啉骨架;當以呋喃-2-甲醇代替芐醇反應時通過O-H插入,[3,3]重排合成保留呋喃骨架的α-氨基酮化合物,并對呋喃骨架進行了進一步轉化。同時利用1,3-二羰基化合物作為烯醇的等價物與N-磺�；�-1,2,3-三氮唑在銠催化下合成吡咯及烯胺化合物。對于鏈狀1,3-二羰基化合物,經歷O-H插入,VA唑中間體,最終生成吡咯化合物;對于C2無取代的環(huán)狀1,3-二羰基化合物,反應優(yōu)先發(fā)生在其相應烯醇式的C2位,最終生成并環(huán)的吡咯化合物;當C2被甲基取代時則經歷O-H插入,VA唑中間體,在環(huán)張力的阻礙下停留在烯胺化合物。論文共分四個章節(jié)。第一章介紹了三氮唑化學的發(fā)展現(xiàn)狀第二章提出了本論文的選題依據(jù)。第三章研究了三氮唑與芐醇及呋喃甲醇的反應第四章研究了三氮唑與1,3-二羰基化合物的反應
[Abstract]:As a kind of very important intermediate of organic synthesis, metal carbene plays an important role in organic chemistry. In recent years, N-sulfonyl-1,2,3-triazole, as a chemically efficient, safe and environmentally friendly precursor of 偽-imidacabine, has received extensive attention. The 偽-imine metal carbines produced by the reaction of rhodium-based metal catalysts can be obtained by cyclopropane reaction, C, H, etc. A series of nitrogen-containing skeleton compounds were constructed by insertion reactions such as O-H, N-H and other types of carbene-related reactions. Our team has successfully constructed pyrrole and pyrazine skeletons through N-sulfonyl-1,2,3-triazole. On the basis of our previous work, we have developed a rhodium-catalyzed N-sulfonyl-1,2,3-triazole and benzyl alcohol through O-H insertion and [1,3] rearrangement to produce 偽-amino ketone compounds. The polysubstituted dihydroisoquinoline framework was further constructed by Pictet-Spengler reaction. When furan-2-methanol was used to replace benzyl alcohol, 偽-amino ketone was synthesized by [3,3] rearrangement and the furan skeleton was further transformed. Pyrrole and enamine compounds were synthesized by using 1,3-dicarbonyl compounds as the equivalent of enol and N-sulfonyl-1,2,3-triazole under the catalysis of rhodium. For chain 1, 3-dicarbonyl compounds, through O ~ (2 +) H insertion, the intermediates of VA were used to form pyrrole compounds. For C2-unsubstituted ring-1,3-dicarbonyl compounds, the reaction takes place at the corresponding enol-type C2 site, resulting in the formation of pyrrole compounds. When C2 is substituted by methyl, it goes through O ~ (2) H insertion, the intermediate of VA, which stays in the enamine compound under the hindrance of ring tension. The thesis is divided into four chapters. The first chapter introduces the development of triazole chemistry. The second chapter puts forward the basis of this thesis. In chapter 3, the reaction of triazole with benzyl alcohol and furan methanol is studied. In chapter 4, the reaction of triazole with 1,3-dicarbonyl compounds is studied.
【學位授予單位】：東北師范大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O621.25
本文編號：2462847
[Abstract]:As a kind of very important intermediate of organic synthesis, metal carbene plays an important role in organic chemistry. In recent years, N-sulfonyl-1,2,3-triazole, as a chemically efficient, safe and environmentally friendly precursor of 偽-imidacabine, has received extensive attention. The 偽-imine metal carbines produced by the reaction of rhodium-based metal catalysts can be obtained by cyclopropane reaction, C, H, etc. A series of nitrogen-containing skeleton compounds were constructed by insertion reactions such as O-H, N-H and other types of carbene-related reactions. Our team has successfully constructed pyrrole and pyrazine skeletons through N-sulfonyl-1,2,3-triazole. On the basis of our previous work, we have developed a rhodium-catalyzed N-sulfonyl-1,2,3-triazole and benzyl alcohol through O-H insertion and [1,3] rearrangement to produce 偽-amino ketone compounds. The polysubstituted dihydroisoquinoline framework was further constructed by Pictet-Spengler reaction. When furan-2-methanol was used to replace benzyl alcohol, 偽-amino ketone was synthesized by [3,3] rearrangement and the furan skeleton was further transformed. Pyrrole and enamine compounds were synthesized by using 1,3-dicarbonyl compounds as the equivalent of enol and N-sulfonyl-1,2,3-triazole under the catalysis of rhodium. For chain 1, 3-dicarbonyl compounds, through O ~ (2 +) H insertion, the intermediates of VA were used to form pyrrole compounds. For C2-unsubstituted ring-1,3-dicarbonyl compounds, the reaction takes place at the corresponding enol-type C2 site, resulting in the formation of pyrrole compounds. When C2 is substituted by methyl, it goes through O ~ (2) H insertion, the intermediate of VA, which stays in the enamine compound under the hindrance of ring tension. The thesis is divided into four chapters. The first chapter introduces the development of triazole chemistry. The second chapter puts forward the basis of this thesis. In chapter 3, the reaction of triazole with benzyl alcohol and furan methanol is studied. In chapter 4, the reaction of triazole with 1,3-dicarbonyl compounds is studied.
【學位授予單位】：東北師范大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O621.25
【參考文獻】
相關期刊論文 前2條
1 吳學宏,李飛武,張文華,劉鵬飛,鄭樂,劉西莉;咯菌腈對西瓜幼苗生長及抗病性相關酶活性的影響[J];植物病理學報;2004年06期
2 王福東,李謙和,彭東明;莫西沙星合成方法[J];藥學進展;2003年04期
相關碩士學位論文 前1條
1 鄭光范;N-氟代雙苯磺酰亞胺與炔烴的自由基串聯(lián)反應研究[D];東北師范大學;2014年
，本文編號：2462847
本文鏈接：http://sikaile.net/shoufeilunwen/gckjbs/2462847.html
教材專著
