骨架上含三個氧原子之含氧籠狀化合物之面向選擇性及化學轉換之研究

Abstract

本論文以雙醇化合物4進行臭氧裂解反應，合成出骨架上含有三個氧原子且apex碳上具有烯基及羰基之籠狀化合物9及10。 利用apex碳上具有烯基及羰基之籠狀化合物9及10進行親電子性反應及親核性反應，探討反應之立體面向選擇性，皆得到高比例之anti-attack產物。 以雙醇化合物22及25進行臭氧裂解反應，合成出骨架上含有三個氧原子之含氧籠狀化合物23及26。以化合物23及26進行化學轉換反應可得到重排產物29及30；若和Lawesson's Reagent反應，可得到骨架上含硫之雜環籠狀化合物32及33。 利用雙醇化合物22及25進行臭氧裂解反應，隨之加入n-butylamine，便可得到骨架上含氮之雜環籠狀化合物34及35。

The synthesis of the diacetal trioxa-cage compounds 9 and 10 with alkene group or carbonyl group on the apex carbon have been accomplished from ozonolysis of diol compounds 4. Reaction of the trioxa-cages 9 and 10 with electrophiles and nucleophiles exclusively gave the corresponding anti-attack products. The synthesis of the diacetal trioxa-cage compounds 23 and 26 have been accomplished from ozonolysis of diol compounds 22 and 25. Reaction of 23 and 26 with TiCl4 in dichloromethane gave the hydride rearrangement products 29 and 30. Reaction of 23 and 26 with Lawesson's Reagent in dichloromethane gave the transformation products 32 and 33. Ozonolysis of diols then adding n-butylamine gave the diacetal dioxamonoaza-cages 34 and 35.