22 [3+2]付加環化反応を用いた生理活性化合物の合成(口頭発表の部)

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A dipolar trimethylenemethane (TMM) generated thermally from a 1,1-dialkoxy-2-methylenecyclopropane is an useful three-carbon 1,3-dipole for the [3+2] cycloaddition reaction. It reacts with an electron deficient olefin or an oxime to afford a five-membered carbo- and heterocycle. We report here the syntheses of natural and unnatural biological active compounds based on the [3+2] cycloaddition of the TMM. 1. Synthesis of (±)-allokainic acid Kainoid, as exemplified by kainic acid, is a potent agonist of the glutamate receptor. We synthesized allokainic acid by using the [3+2] cycloaddition of the TMM derived from 1 and methyl glyoxylate O-benziloxime. 2. Synthesis and biological activity of fullerene carboxylic acid Although the chemical behavior of fullerenes has suggested possible biological activity of fullerenes, there has been no direct evidence of such activity. We synthesized a water miscible fullerene, and found that it shows distinct biological activity under light irradiation. The water miscible fullerene carboxylic acid 16 was prepared by the [3+2] cycloaddition of a dipolar TMM with C_<60> followed by esterification of the resultant fullerene alcohol 14 with succinic anhydride. The carboxylic acid 16 showed distinct biological activity, e.g. cytotoxicity, enzyme inhibitory activity, and DNA cleaving activity under irradiation of low-energy visible light.
天然有機化合物討論会の論文
1993-09-10