葉名倉Ming-Chang P. Yeh曹文正Wen-Cheng Tsao2019-09-04不公開2019-09-042006http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22GN0891420122%22.&%22.id.&http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/101010本論文共分成四部份: 以鈀(0)催化分子內異核環化反應,使g位置帶有三級醇之共軛雙烯化合物與芳香烴溴化物行加成反應,得到單一非鏡像立體選擇性異構物。反應可經由兩種途徑來解釋,帶羥基之環形共軛雙烯可得1,4-oxyarylation產物;帶羥基之非環形共軛雙烯可得1,2-oxyarylation產物。 以鈀(0)催化分子內環丙烷化反應,使帶有雙羰基之共軛雙烯化合物與乙烯溴化物反應,得到單一非鏡像立體選擇性異構物。反應得到雙環[4.1.0]庚烯衍生物。 以二氯化鉑為催化劑,在醇為溶劑中行分子內炔與共軛雙烯之環化反應,得到單一非鏡像立體選擇性的聯結雙環醚化合物。 以金離子催化帶有芳香炔的雙烯進行分子內環化異構化反應,得到單一非鏡像立體選擇性異構物。反應在起始物芳香環上沒有強拉電子基情況下,得到芳香環進行親電子性加成的產物。反應在起始物芳香環上有強拉電子基或缺乏芳香環的情況下,得到1,3,6-三烯環形化合物。Palladium-catalyzed reaction of aryl bromides with 7-hydroxy-1,3-dienes proceeded in different reaction paths depending on the structure of the starting substrates. With cyclic 7-hydroxy-1,3-dienes, the reaction proceeded in the 1,4-alkoxyarylation fashion. While with acyclic 7-hydroxy-1,3-dienes, the reaction produced 1,2-alkoxyarylation products. Palladium(0) catalyzed intramolecular cyclization of cyclohexa-1,3-diene bearing a diketo functionality at C-5 yielded bicyclo[4.1.0]heptene derivative with the vinyl group at the C-1 position of the ring. Platinum(II) chloride catalyzed intramolecular cyclization of cyclohexa-1,3-diene bearing a terminal alkynyl side chain in alcoholic solvent afforded bicyclo[4.3.0]nonene derivative with an alkoxy group at C-4 position of the bicyclic ring. Gold(I) intramolecular cyclization of cyclohexa-1,3-diene bearing a terminal phenyl alkyne produce tetracyclic compounds. While an electron-withdrawing group present at the phenyl, cyclization produced fused bicyclic skeletons.13-雙烯分子內環化反應金屬催化1,3-雙烯與官能基之分子內環化反應