四氢叶酸模型化合物咪唑啉盐的基团转移反应

Groups Transfer Reaction of Imidazolinium Salts as Tetrahydrofolate Model Compounds

合成了2种四氢叶酸辅酶模型化合物咪唑啉盐7和8.它们与双官能团亲核体作用,分别完全转移了3个和5个碳单元;化合物7与单官能团亲核体作用,部分转移了3个碳单元;以部分转移产物化合物17作为四氢叶酸甲醛态模型,与胺类反应实现了带硝基的4个碳单元的完全转移;并研究了模型化合物7的还原反应.这些反应模拟并扩展了四氢叶酸辅酶在生物体内转移一碳单元的功能,产生了几种新的合成方法和试剂,可以应用于有机合成中.

Tetrahydrofolate （THF） coenzyme is the methyl source of the methylation for many materials （ including the DNA and RNA） in the living body to transfer one carbon unit for the biosynthesis and metabolism. The study on mimicking the characteristics of the THF coenzyme can contribute significantly to our understanding of the mechanism of action of the coenzymes themselves and provide a valuable effective reagents for groups transfer reaction for practical utility. Owing to such interests, two kinds of imidazolinium iodides 7 and 8 were prepared as the tetrahydrofolate model compounds at the oxidation level of formate, which reacting with bifunctional nucleophiles led to three or five carbon fragments be transferred completely and compound 7 reacts with monofunctional nucleophiles to afford the products transferred part of three carbon fragments. When the reaction of compound 17 as formaldehyde oxidation levels model compound of THF with amines carried out, the four carbon fragments with nitro were completely transferred. The reduction of model compound 7 was also studied. The procedure have mimicked and expanded the function of biochemical transfer of one carbon fragment of the tetrahydrofolate coenzyme and produced some new synthesis methods and reagents which can be applied to organic synthesis.