MOLECULAR DESIGN OF FUNCTIONALIZED HEHEROCYCLIC COMPOUNDS

该项目旨在开发功能化杂环化合物的合成途径。所得结果如下：1.以镁盐和DBU处理5-甲酰基-1,3,6-三甲基-2,4(1H,3H)-嘧啶二酮为原料，合成了5,6-二氢-5,6-二（亚甲基）-2,4(1H,3H)-嘧啶二酮中间体。烯醇酯与烯烃进行了[4 + 2]环加成反应，具有高度的区域选择性和立体选择性。用同样的方法，得到了4(1H)-吡啶酮和DELTA^3-唑啉-5-酮体系中的烯醇化物，并研究了这些烯醇化物的环加成反应生成喹啉和吲哚。2.6-烯基氨基-5-甲酰基-1,3,6-三甲基-2,4(1H,3H)-嘧啶二酮与α -氨基酸衍生物的反应产生分子内亚甲酰基加合物和烯反应产物。反应路径取决于氨基酸的性质；与n取代的氨基酸衍生物反应得到亚甲酰亚胺中间体。另一方面，与n -未取代氮的反应得到亚胺作为中间体，亚胺-烯反应生成融合氮平类化合物。在2(1H)-吡啶酮、铬酮和吡啶嘧啶体系的反应中也发现了类似的隐匿性。3.功能化碳二酰亚胺被用作杂环体系如吡啶、嘧啶和咪唑的合成构件。

This project has been directed toward the development of synthetic accesses to functionalized heterocyclic compounds. The results obtained are demonstrated as belows; 1.A 5,6-dihydro-5,6-bis(methylene)-2,4(1H,3H)-pyrimidinedione intermediate was generated by the treatment of 5-formyl-1,3,6-trimethyl-2,4 (1H,3H)-pyrimidinedione with magnesium salt and DBU. The enolate underwent[4 + 2]cycloaddition reaction with olefins in highly regio-and stereoselective manners. By similar methods,enolates in 4(1H)-pyridone and DELTA^3-phrazolin-5-one systems were obtained and the cycloaddition reactions using these enolates leading to quinolines and indazoles were investigated. 2.The reaction of 6-alkenylamino-5-formyl-1,3,6-trimethyl-2,4(1H,3H)-pyrimidinedione with alpha-amino acid derivatives afforded intramolecular azomethine ylide adducts and ene reaction products. The reaction paths depended on the nature of the amino acids;the reaction with N-substituted amino acid derivatives gave azomethine ylide intermediates. On the other hand,the reaction with N-unsabstituted ones gave the imines as intermediates,which underwent imine-ene reaction to form fused azepines. Similar bident reaction profiles were elucidated in the reactions of 2(1H)-pyridone,chromenone,and pyridopyrimidine systems. 3.Functionalized carbodiimides were used as a synthetic building block for heterocyclic systems such as pyridine,pyrimidine,and imidazole.