臺灣博碩士論文加值系統

在釕金屬錯化合物 Ru(COD)(COT) (26) 的催化下,可將雙環[2.2.1]庚二
烯偶合成具有三環戊烷架構的雙烯化合物 (28). 在臭氧化及三苯基磷氫
硼化鈉的還原反應後,即可得到具有三環戊烷架構的衍生物 (30-32). 化
合物 (30) 使用碳酸銀-矽藻土試劑可以選擇性的對鄰位槍機內醚化合物
(30) 中之槍基做氧化反應得到內酯化合物以此化合物為基礎可以進一步
合成三環戊烷衍生物 (35) 及 (36).

另外,我們也利用三環戊烷架構的雙烯化合物 (28) 和 N-溴丁二內亞醯在
水及二甲亞偑中作用,得到了一些有趣的化合物 (39),(40),(41) ,我們由
推測的反應機構及實驗結果數據,來說明這些化合物的生成,而對於要合成
一個碗型結構化合物(42a)的實驗並沒有成功.

Norbornadiene was dimerized to give a pentaquinane derivative
(28) through the mediation of the ruthenium complex (26). The
ozonolysis of compound (28) followed by the addition of
triphenylphosphine and sodiumborohydride gave a mixture of
butyrlactol (30), tetrahydropyran (31) and tetraol (32). The
lactone (33), formed from the oxidation of lactol (30) with Ag2
CO3-Celite, was converted to triquinane derivative (36) in two
stepssequences. Compound (36) was characterized by a three-
membered rith moiety formed from the skeletal rearrangement.
Treament of diene (28) with N-bromrsuccimide in a mixture of
DMSO and water to give a mixture of dibromide (39) and (40).
Compound (40) was formed from the bromohydrin formation followed
by intramolecular cyclization. Its single crystral structure was
determined unambiguously by X-Ray diffraction. Finally, the
attempt to prepare the the bowl-shaped molecule (42a) is fail.