骨架含二個及三個氧原子之含氧籠奘狀化合物之合成及其面向選擇性

Abstract

本論文對 bis-endo-diol 取代基之 [2.2.1]庚烯衍生物，經由臭氧裂解反應，可合成出骨架上含有三個氧之籠狀化合物。 對 bis-endo-diol 取代基之 [2.2.2]辛烯衍生物及單環己烯衍生物，經由臭氧裂解反應，可合成出單環環化產物。 將 1,4- 對苯菎衍生物與 1,3- 環戊二烯及 1,4- 環己二烯進行 Diels-Alder 反應，將其所產生的 endo 加成產物，使用 NaBH4-CeCl3 試劑進行立體選擇性還原反應，再將此產物經由臭氧裂解反應，可合成出骨架上含有三個氧與雙鍵之籠狀化合物。 本論文利用臭氧裂解反應可合成出籠狀化合物 57。 本論文利用碘誘導環化反應，再經由臭氧裂解反應可合成出籠狀化合物 67、76。 本論文對籠狀化合物 57、67、76 進行面向選擇性研究。

Several novel diacetal teioxa-cages compounds 4, 9a-9c, 14 and 17 are synthesized in a short sequence. Diacetal trioxa-cage where synthesized from norbornene derivative of bis-endo-diol by utilizing a novel ozonolysis reaction as the key step. Ozonolysis of bicyclo[2.2.1]heptenes 3, 8a-8c, 13 and 16in dichloromethane at -78℃ followed by reduction with dimethyl sulfide gave diacetal oxa-cages 4, 9a-9c, 14 and 17 in moderate yields, respectively. Ozonolysis of bicyclo[2.2.2]octene 19 under the same reaction conditions gave mono-cyclization product 20. Ozonolysis of cyclohexene 29 under the same reaction conditions gave mono-cyclization product 32. Ozonolysis of p-benzoquinones derivatives 34 ,37 and 40 under the same reaction conditions gave diacetal oxa-cages 35 ,38 and 41 in moderate yields, respectively. Synthesis of carbonyl oxa-cage 57 is by using ozonolysis reaction. Synthesis of carbonyl oxa-cages 67 and 76 is by using iodocyclization reaction. The facial selectivity of dioxa-cages and trioxa-cage is high selectivity.