MOLECULAR DESIGN OF FUNCTIONALIZED HEHEROCYCLIC COMPOUNDS

该项目一直致力于开发功能化杂环化合物的合成途径。1.以5-甲酰基-1，3，6-三甲基-2，4（1H，3 H）-嘧啶二酮为原料，经镁盐和DBU处理，得到5，6-二氢-5，6-二亚甲基-2，4（1H，3 H）-嘧啶二酮中间体。烯醇化物与烯烃发生[4 + 2]环加成反应，具有高度的区域和立体选择性。通过类似的方法，在4（1H）-吡啶酮和Δ ^3-吡唑啉-5-酮体系中得到了烯醇化物，并研究了这些烯醇化物与喹啉和吲唑的环加成反应。2. 6-烯氨基-5-甲酰基-1，3，6-三甲基-2，4（1H，3 H）-嘧啶二酮与α-氨基酸衍生物反应，得到分子内甲亚胺叶立德加合物和烯反应产物。反应途径取决于氨基酸的性质;与N-取代的氨基酸衍生物的反应得到甲亚胺叶立德中间体。另一方面，与N-未取代的反应得到作为中间体的亚胺，其进行亚胺-烯反应以形成稠合氮杂卓。在2（1H）-吡啶酮，色烯酮和吡啶并嘧啶体系的反应中阐明了类似的双齿反应曲线。3.官能化的双酰亚胺被用作杂环体系如吡啶、嘧啶和咪唑的合成结构单元。

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.