共軛雙烯的分子內環氧與胺的環化反應

林兆駿(Zhao-Jun Lin)

指導教授 ： 葉名倉

國立臺灣師範大學/理學院/化學系/碩士(2006年)

摘要

利用(η5-1,3-環己雙烯)三羰鐵陽離子錯鹽以及(η5-1,3-環庚雙烯)三羰鐵陽離子錯鹽與帶有氰基之鋅銅試劑進行親核性加成反應，再以氧化劑將三羰鐵錯合物去錯合，並將氰基轉換為環氧基，將此環氧共軛雙烯化合物利用路易士酸 BF3?OEt2 進行分子內環化反應，產生三環或架橋化合物。

利用(η5-1,3-環庚雙烯)三羰鐵陽離子錯鹽，與sodium diphenylacetonitrile 進行親核性反應，經氧化劑去錯合後，得到C-5位置帶有雙苯官能基之1,3-環庚雙烯氰化合物，並將氰基轉換為苯磺醯胺化合物，將此共軛雙烯苯磺醯胺化合物利用0.05 當量的 Au(PPh3)Cl及0.05 當量的AgOTf溶於甲苯溶劑中進行分子內氫胺化反應，得到單一位向選擇的雜環化合物。

關鍵字

環氧

並列摘要

Abstract

Addition of cyano-funtionalized zinc-copper reagents to (η5-cyclohexa-1,3-diene)Fe(CO)3 and (η5-cyclohepta - 1,3-diene )Fe(CO)3 complexes produce the corresponding C-5 cyano- funtionalized (η4- cyclohexa
-1,3-diene)Fe(CO)3 and (η4-cyclohepta-1,3-diene)Fe(CO)3 complexes, respectively. Transformation of the cyano group using trimethylsulfonium iodide and base to give epoxide group. Intramolecular cyclization of diene with epoxide catalyzed by BF3．OEt2 afforded hetero-tricyclic compounds.

The addition of sodium diphenylacetonitrile to (η5-cyclohepta-1,3-diene)Fe(CO)3 cation followed by decomplexation with cerium( IV ) ammonium nitrate (CAN) procedured the C-5 diphenylacetonitrile substituted cyclic 1,3-dienes. The resulting diphenylacetonitrile dienes was treated with lithium aluminium hydride, followed by addition of benzenesulfonyl chloride under basic condition to generate N-(2-(cyclohexa-2,4-dienyl)-2,2-diphenylethyl) benzenesulfonamide derivatives. Gold(I) catalyzed intramolecular cyclization of cyclohexa-1,3-diene bearing a benzenesulfonamide produced indole compounds.

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