含氧籠狀化合物與三甲基丙烯矽烷及三乙基矽烷之親核取代反應之研究

Abstract

本論文利用骨架上含三個氧原子之籠狀化合物4、10、14及23、28與三甲基丙烯矽烷及三乙基矽烷進行雙親核性取代反應，可分別得到進行雙親核取代反應之產物5、6、11、15及24、25與29、30，它們可經由H,H-COSY及NOE光譜實驗判斷其立體化學。 以雙醇化合物17進行臭氧裂解反應，可得骨架上含有四個氧原子之籠狀化合物18，加入三甲基丙烯矽烷進行親核性取代反應可得線型之trioxatriquinane骨架之衍生物19。 利用骨架上含有縮酮基之含氧籠狀化合物32進行親核性取代反應，發現僅可得到單取代之產物33、34，它們的立體化學結構係由反應機構來推斷，唯須進一步之求證。

Abstract The reaction of the trioxa-cage compounds 4, 10, 14, 23, 28 with allyltrimethylsilane and triethylsilane gave the corresponding compounds 5, 6, 11, 15, 24. Their stereochemistry can be determined by H,H-COSY and NOE experiments. Ozonolysis of the diol compound 17 gave the tetraoxa-cage compound 18. Doubled nucleophilic substitution reaction of 18 with allyltrimethylsilane gave linear trioxatriquinane derivative compound 19. The double nucleophilic substitution reactions of oxa-cage compound 32, only gave mono-substituted products 33, which stereochemistry was proposed on the basis of the reaction mechanism.