鉑(II)金屬催化雙烯與炔之分子內環化反應

鄭紹廷

指導教授 ： 葉名倉

國立臺灣師範大學/理學院/化學系/碩士(2005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sodium dimethylmalonate或sodium-2,4-pentadionate等親核試劑反應，所得三羰鐵錯合物經CAN氧化去三羰鐵後，得到C-5位置帶有雙酯或雙酮官能基之1,3-環形雙烯化合物。

將帶雙酯官能基之1,3-環形雙烯化合物在鹼性條件下與3-溴丙炔反應，可得C-5位置帶有雙酯官能基之1,3.-環己雙烯炔或1,3-環庚雙烯炔之衍生物。在相同反應條件下，亦可以合成出帶雙酮官能基之1,3-環己雙烯炔或1,3-環庚雙烯炔衍生物。

以醇類為溶劑，用二氯化鉑催化帶雙酯官能基之1,3-環己二烯炔或1,3-環庚二烯炔進行分子內環化反應，可得在C-4位置帶有烷氧基之聯結雙環[4.3.0]雙烯以及聯結雙環[5.3.0]雙烯衍生物。然而，利用二氯化鉑催化帶雙酮官能基之1,3-環己雙烯炔進行分子內環化反應，藉由乙醯基加成至環內雙烯可得架橋三環化合物。

關鍵字

鉑(II)金屬催化雙烯與炔之分子內環化反應

並列摘要

The addition of sodium dimethylmalonate or sodium-2,4-pentadionate to (η4-cyclohexa-1,3-diene)Fe(CO)3 cation and (η4-cyclohepta-1,3-diene)Fe(CO)3 cation followed by decomplexation with cerium ammonium nitrate (CAN) proceduced the C-5 diester and diketo substituted cyclic 1,3-dienes.

The resulting diester dienes was treated with propagyl bromide in basic condition to generate 5-(1,1,-diester-3-alkynyl)cyclohexa-1,3-diene derivatives. Diketo cyclohexadienes and seven-membered analogs were also synthesized under the same reaction conditions.

Platinum(II) chloride catalyzed intramolecular cyclization of 5-(1,1,-dicarbethoxy-3-alkynyl)cyclohexa-1,3-diene and cyclohepta-1,3-diene analogs in alcoholic solvent afforded bicyclo[4.3.0]nonene and bicyclo[5.3.0]decene derivatives with an alkoxy group at C-4 position of the fused bicyclic ring. However, Intramolecular cyclization of 5-(1,1,-diacetyl-3-alkynyl)- cyclohexa-1,3-diene using Pt(II) chloride resulted in addition of a acetyl at the internal position of diene to furnish a bridged tricyclic compound.