葉名倉白蕙棻2019-09-04不公開2019-09-042010http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22GN0896420103%22.&%22.id.&http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/101063　　本文共有三個主題，分別為探討利用鈀金屬催化環丙烷之合成、金陽離子催化螺旋化合物之合成及分子內nitrile oxide與環形烯醇的1,3-偶極環化加成反應。 　　我們利用鈀金屬催化帶有雙酮基的1, 3-環己共軛雙烯及苯乙烯溴化物使形成環丙烷的結構，為單一非鏡像異構物。鈀金屬Pd(PPh3)4 先與苯乙烯溴化物配位形成鈀(II)的離子，再與碳酸銀結合形成鈀陽離子錯合物，此時鈀陽離子配位於酮基的氧上後使α位置氫的酸性增加而可以讓碳酸鉀拔除，再由下方同向接上雙烯位置，最後還原除去後我們可得到具有立體選擇性的雙環[4.1.0]庚烯衍生物。 利用金與銀共催化系統催化帶有炔基的烯醇化合物，經Claisen-type rearrangement形成了帶有雙鍵及酮基的螺旋化合物，不但反應時間快速，室溫條件及極高的產率也為此反應主要的優點，但是產物為一組非鏡像異構物，因此藉由氫化反應將雙鍵還原得到單一非鏡像異構物。 　　將帶醛肟的烯醇衍生物，以N–氯丁二內亞醯胺（NCS）和三乙基胺為環化條件，進行分子內環化加成反應，得到單一位向選擇性的nitrones衍生物或isoxazolines衍生物。There are three parts in this article. The first is synthesis of bicyclo[4.1.0]heptenes via palladium-catalyzed reaction of β-styryl bromides with 3-(cyclohexa-2,4-dienyl)pentane-2,4-dione. The second is synthesis of spirocyclic ketones via gold(I)-catalyzed Claisen-type rearrangement of cyclic 8-aryl-2,7-enyn-1-ols. The last is intramolecular 1,3-dipolar cycloaddition of nitrile oxide with cyclic allylic alcohol. Palladium-catalyzed intramolecular coupling-cyclization of 3-(cyclohexa-2,4-dienyl) pentane-2,4-dione with β-styryl bromides proceeds in regio- and stereoselective fashions to give 2-styryl-substituted bicyclo[4.1.0]hept-3-enes in good yields. The formation of the bicyclo[4.1.0] hept-3-enes was rationalized by starting with oxidative addition of Pd(PPh3)4 to the carbonbromine bond of bβ-styryl bromide (RBr) to give Pd(R)BrL. Reaction of Pd(R)BrL with Ag2CO3 generates a cationic RPd(II)L species. The postulated bicyclic hη1-allylpalladium intermediate leads to 2-styryl-substituted bicyclo[4.1.0]hept-3-enes with exclusive regio- and stereoselectivities after reductive elimination. The gold(I)-catalyzed Claisen-type rearrangement of cyclic 8-aryl-2,7-enyn-1-ols proceeds via a cationic allylic vinyl ether gold intermediate to give spirocyclic ketones. The reaction proceeded via attack of the hydroxyl group onto the gold-activated alkynes followed by [3,3]-sigmatropic rearrangement to generate the spirocyclic ketones. The oxime derivatives were treated with N-chlorosuccinimide and triethylamine in CH2Cl2 to afford nitrone dericatives or hetero tricyclic compounds via intramolecular cycloaddition.環丙烷螺旋化合物13-偶極環化加成