Title: 骨架上含兩個氧原子之含氧籠狀化合物之面向選擇性研究及骨架上具兩個甲醚基之含養籠狀化合物之重排反應
π-Facial Selectivity of Dioxa-cages and Chemical Transformation of Dioxa-cages
Authors: 鐘惠雪
Hui-Hsueh Chung
Hsien-Jen Wu
Keywords: 重排;面向選擇;籠狀化合物;酸性樹酯;rearrangement;Facial Selectivity;cage;Amberlyst-15
Issue Date: 2000
Abstract: 本論文成功的以化合物8及化合物23為起始物經Wittig 反應,合成出骨架上含有的兩個氧的籠狀化合物15及24。 利用籠狀化合物8進行親電子性及親核性反應,探討反應之立體面向選擇性,發現其以syn-attack為主產物。 將diols 30,35,39,42,47,51 溶於甲醇中,在-78℃下進行臭氧裂解反應可得化合物31,36,40,43, 48,52. 在Amberlyst-15的作用下可成功使化合物31, 36, 40, 43, 48, 52及2,5-Dimethoxy-2,5-dihydrofuran (mixture of cis and trans isomers)進行重排反應,進而得到其重排產物。 Amberlyst-15與TiCl4相較下為一溫和、不具危險性且方便、便宜之試劑,其為固體顆粒,欲終止反應時,僅需經由過濾即可移除之。
π-Facial Selectivity of Dioxa-cages and Chemical Transformation of Dimethoxy Dioxa-cages Student:Hui-Hsueh Chung Advisor:Dr. Hsien-Jen Wu Institute of applied Chemistry Nationl Chiao Tung University Abstract The diacetal dioxa-cage compounds15 and 24 from Wittig reaction of compounds 8 and 23 was synthesized successfully. The reaction of the diacetal dioxa-cage compounds 8 with electrontrophiles gave the corresponding syn-sttack products. Ozonlysis of diols 30,35,39,42,47,51 in MeOH at -78℃follow by treatment with Me2S and Amberlyst-15gave compounds31,36,40,43, 48 ,52. The reaction of the compounds 31, 36, 40, 43, 48, 52and 2,5-Dimethoxy-2,5-dihydrofuran (mixture of cis and trans isomers)with Amberlyst-15 in dichloromethane gave the hydride rearrangement products. Amberlyst-15 compare with TiCl4 is a mild、saft、low-priced and convenience catalyst and work-up is exceedingly simply, it only involves filtration of the resin and removel of solvent to obtain product.
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