Studies on the Development of Practical Electroorganic %reactions Associated with Biological Processes

利用易于从天然生物物质中获得的手性构建块是当前合成生物活性化合物的主题。本研究项目涉及(A)手性生物质的电化学转化为多用途手性合成子及其合成应用，以及(B)通过电化学手段将生化生产的青霉素衍生物转化为有价值的头孢菌素化合物及其应用。在研究项目(A)中，我们开发了一种基于电有机反应的高效官能团制备方法，即硒-脱硒序列，(2)氧化烷的选择性环重排，(3)四氧化钌介导的醇氧化，(4)卤素介导的呋喃环裂解等。这些方法的合成效用显示在有用的生物活性化合物的合成上，如从醋酸脱氢lynalilyl合成卡拉哈烯酮和从(+)-3-蒈烯合成菊花酸等。在第二个研究项目(B)中，我们成功地对氮杂二酮的戊烯基部分进行了选择性烯型氯化。该程序已扩展到各种头孢菌素类似物的实际合成中。研究了3′-氯头孢菌素转化为相应的3-亚甲基头孢菌素。

Use of chiral building blocks easily accessible from natural bio-mass is of current topics in the synthesis of bio-active compounds. This research project concerns with (A) electrochemical transformations of chiral bio-mass into versatile chiral synthons and their synthetic applications and (B) conversion of biochemically produced penicillin derivatives into the valuable cephalosporin compounds by electrochemical means and their applications. In the research project (A), we developed an efficient functional group preparing methods based on electoorganic reactions, i.e. selenation-deselenation sequence, (2) selective ring rearrangement of oxiranes, (3) ruthenium tetraoxide mediated oxidation of alcohols, (4) halogen mediated ring cleavage of furans, and others. Synthetic utilities of these methodologies are shown in the synthesis of useful bio-active compounds such as karahanaenone from dehydrolynalilyl acetate and chrysanthemic acids from (+)-3-carene, and others. In second research program (B), we have succeeded in the selective ene-type chlorination of prenyl moiety of azetidinones. The procedure has been extended in the practial synthesis of a variety of cepharosporin analogues. Conversion of 3'-chlorocephalosporins into the corresponding 3-methylenecephams is also investigated.