利用化學解析法來合成掌性四氧四縮醛之含氧籠狀化合物

Abstract

中文摘要 本論文分別利用雙環[2.2.1]庚烯衍生物，來進行臭氧裂解反應，合成出骨架上含有四個氧原子且側鏈具酯基之含氧籠狀化合物4和10，經水解後，成功地合成出側鏈具羥基之含氧籠狀化合物5和11。 利用側鏈具羥基及甲基之含氧籠狀化合物，進行一系列取代反應，成功地合成出側鏈取代基具硫化物、胺類、疊氮等不同官能基之含氧籠狀化合物 12, 13, 14, 15, 16, 17, 18 及20，另外亦順利地合成出雙含氧籠狀化合物21。 利用側鏈具羥基之含氧籠狀化合物，經化學解析法及動力學解析法，成功地合成出掌性含氧籠狀純物質。 本論文利用側鏈具硫代醚基及亞□基之含氧籠狀化合物13, 14, 28和29，來代替二甲基硫醚及DMSO試劑，進行Corey Kim氧化反應及Swern氧化反應，對一級醇、二級醇作氧化試驗。

Abstract Oznolysis of bis-endo-g-keto of bicyclo[2.2.1]heptene derivatives in CH2Cl2 at -78℃ following by treatment with Me2S afforded different tetraoxa-cage compounds with ester group on the side chain. After hydrolysis, different oxa-cages with hydroxy group on the side chain can be obtained. Using the oxa-cage compounds with hydroxy and methyl groups on the side chain via a series of substitution reactions, we can synthesize oxa- and bisoxa-cages with different functional group (such as azido, sulfide and amino groups) on their side chains. The synthesis of chiral oxa-cage compounds has been accomplished by chemical and enzymatic resolutions. Attempts for the applications of oxa-cages 13, 14, 28 and 29 on Corey-Kim oxidation and Swern oxidation to primary and secondary alcohols have been made.