α-亚胺铑卡宾与醇、1,3-二羰基化合物的反应研究
发布时间：2019-04-22 12:44
【摘要】：金属卡宾作为一类非常重要的有机合成中间体在有机化学中有着重要地位。近年来,N-磺酰基-1,2,3-三氮唑作为一种化学高效、安全、环境友好α-亚胺卡宾前体受到人们广泛关注。其在以铑为主的金属催化剂的作用下产生的α-亚胺金属卡宾体可以通过环丙烷化反应、C-H、O-H以及N-H等插入反应以及其他类型卡宾参与的反应来构建一系列含氮骨架化合物。我们课题组通过N-磺酰基-1,2,3-三氮唑已经成功构建了吡咯及吡嗪骨架。在我们课题组此前工作基础上发展了一种铑催化N-磺酰基-1,2,3-三氮唑与苄醇经历O-H插入,[1,3]重排合成α-氨基酮化合物,并通过Pictet-Spengler反应进一步构建了多取代二氢异喹啉骨架;当以呋喃-2-甲醇代替苄醇反应时通过O-H插入,[3,3]重排合成保留呋喃骨架的α-氨基酮化合物,并对呋喃骨架进行了进一步转化。同时利用1,3-二羰基化合物作为烯醇的等价物与N-磺酰基-1,2,3-三氮唑在铑催化下合成吡咯及烯胺化合物。对于链状1,3-二羰基化合物,经历O-H插入,VA唑中间体,最终生成吡咯化合物;对于C2无取代的环状1,3-二羰基化合物,反应优先发生在其相应烯醇式的C2位,最终生成并环的吡咯化合物;当C2被甲基取代时则经历O-H插入,VA唑中间体,在环张力的阻碍下停留在烯胺化合物。论文共分四个章节。第一章介绍了三氮唑化学的发展现状第二章提出了本论文的选题依据。第三章研究了三氮唑与苄醇及呋喃甲醇的反应第四章研究了三氮唑与1,3-二羰基化合物的反应
[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 伪-imidacabine, has received extensive attention. The 伪-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 伪-amino ketone compounds. The polysubstituted dihydroisoquinoline framework was further constructed by Pictet-Spengler reaction. When furan-2-methanol was used to replace benzyl alcohol, 伪-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.
【学位授予单位】：东北师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.25
本文编号：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 伪-imidacabine, has received extensive attention. The 伪-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 伪-amino ketone compounds. The polysubstituted dihydroisoquinoline framework was further constructed by Pictet-Spengler reaction. When furan-2-methanol was used to replace benzyl alcohol, 伪-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.
【学位授予单位】：东北师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.25
【参考文献】
相关期刊论文 前2条
1 吴学宏,李飞武,张文华,刘鹏飞,郑乐,刘西莉;咯菌腈对西瓜幼苗生长及抗病性相关酶活性的影响[J];植物病理学报;2004年06期
2 王福东,李谦和,彭东明;莫西沙星合成方法[J];药学进展;2003年04期
相关硕士学位论文 前1条
1 郑光范;N-氟代双苯磺酰亚胺与炔烃的自由基串联反应研究[D];东北师范大学;2014年
，本文编号：2462847
本文链接：https://www.wllwen.com/shoufeilunwen/gckjbs/2462847.html
