6-氧-五環[9.2.2.2.0.0]-十七烷-12,14,16-三烯-12,13-乙酸之合成與面選擇性環化反應

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Title:	6-氧-五環[9.2.2.2.0.0]-十七烷-12,14,16-三烯-12,13-乙酸之合成與面選擇性環化反應
Other Titles:	6-oxa-pentacyclo[9.2.2.2.0.0]-heptadeca-12,14,16-triene-12,13- dicarboxylic anhydride
Authors:	許湘琴 Hsu, Hsiang-Chin
Contributors:	林振東 Liang, Bih-Fong 東海大學應用化學系
Keywords:	狄爾斯-亞德
Date:	1996
Issue Date:	2011-05-25T08:45:05Z (UTC)
Abstract:	雙烯化合物45與乙炔二甲酸二甲酯進行Diels-Alder反應後,生成了雙酯基化合物47,經皂化,脫水便可製造酸化合物49.由於馬林可活化鄰旁的雙鍵,使得此化合物擁有良好的親雙烯性質.再將化合物49與環戊二烯,2,3-二甲基-1,3-丁二烯及化合物28,31,60,63等具環外稠合順-1,3-丁二烯多碳環化合物進行Diels-Alder環化加成反應,可分別生成化合物51 a/51b,62a,64a/64b,68a/68b,69b,70a/70b.從這些產物結構分析初步推測反應會以化合物49中與乙烯橋同側的面(syn)位向進行加成.產物51a具有緯環式[2+2+2]面對面平行軌域. 化合物51a經照光,靠近酸的兩個平行雙鍵會進行[2+2]環化加成反應,得到化合物52a的結構.若進行溴化反應,則會得到1,6-加成產物55,靠近酸的兩個平行雙鍵,為平行跨環碳- 碳鍵形成,而另一邊為交叉跨環碳-碳鍵形成. The Diels-Alder reaction of the ketone 45with dimethyl acetylendicarboxylate produced diester 47, which was then suject to saponification and dehydration to give anhydride 49. Anhydride 49 has good dienophilicity towards cyclopentadiene and polcyclic hydrocarbons with fused exo-cis-1,3-butadienes.The Diels-Alder cycloaddition of 49 with cyclopentadiene, 2,3-dimethyl-1,3-butadiene and compounds 28,31,60,63 produced 51a/51b,62a,64a/64b,68a/68b and70a/70b respectively. The structural analysis of these compounds showed that the Diels- Alder reactions of 49 have high degree of -facial selectivity. The cycloadditions occured at the syn face to the etheno-bridge of 49. Photoreaction of 51a with UV light indicated that the two parallel double bonds near the anhydride unit underwent intramoleccular[2+2] cycloaddition and gave 52a in high yield.1,6-Homconjugative bromination of 51a produced dibromide 55 as the only product; two parallel double bonds near the anhydride unit led to the transannular C-C bridge formation in parallel manner, while the other led to the transannulas C-C bridge formation in cross manner.
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