一、路易士酸輔佐矽保護3-(3-芳香基丙炔基甲苯磺醯胺基)甲基環己-2-烯-1-醇化合物分子內環化反應－含氮螺旋[4.5]癸-6-烯衍生物之合成 二、布忍司特酸催化與路易士酸輔佐2-甲基-2,3-環氧基-4-(3-芳香基丙炔基)環己-1-酮化合物分子內環化反應－7-苯甲醯基雙環[3.2.1]辛-2-酮與芳香基含鹵亞甲基雙環[3.2.1]辛-2-酮衍生物之合成

Abstract

本文分別探討路易士酸（Lewis Acid）輔佐第三丁基二甲基矽保護之3-(3-芳香基丙炔基甲苯磺醯胺基)甲基環己-2-烯-1-醇化合物及布忍司特酸（Brønsted Acids）與路易士酸輔佐2-甲基-2,3-環氧基-4-(3-芳香基丙炔基)環己-1-酮化合物分子內環化反應。論文主要分二部份進行探討，第一部分：利用三氟化硼乙醚作為路易士酸與氟陰離子來源，輔佐第三丁基二甲基矽保護之3-(3-芳香基丙炔基甲苯磺醯胺基)甲基環己-2-烯-1-醇化合物，在室溫，氮氣下，經由分子內環化反應，合成烯氟含氮螺旋[4,5]癸烯衍生物。第二部分：將2-甲基-2,3-環氧基-4-(3-芳香基丙炔基)環己-1-酮分別經由環化反應，在室溫，氮氣下，利用三氟甲磺酸催化合成7-苯甲醯基雙環[3.2.1]辛-2-酮化合物；在室溫，氮氣下，利用路易士酸（三氯化鐵及三氟化硼乙醚）輔佐分別合成烯氯－及烯氟－雙環[3.2.1]辛-2-酮衍生物。This thesis focuses on acid-promoted intramolecular cyclization of O-silyl-protected 3-(3-arylpropargyltosylamino)methylcyclohex-2-en-1-ols and 2-methyl-2,3-epoxy-4-(3-arylpropargyl)cyclohexan-1-ones. Two major reactions are discussed. First, BF3•OEt2-promoted intramolecular cyclization/ fluorination of O-silyl-protected 3-(3-arylpropargyltosylamino)methylcyclo- hex-2-en-1-ols at room temperature under an atmosphere of nitrogen afforded N-containig spiro[4.5]dec-6-ene derivatives containing a C(sp2)-F bond. In this process, boron trifluoride diethyl etherate acts as both the Lewis Acid and the fluoride source. Second, TfOH-catalyzed cyclization of 2-methyl-2,3-epoxy- 4-(3-aryl-propargyl)cyclohexan-1-ones at room temperature under an atmosphere of nitrogen provided 7-benzoylbicyclo[3.2.1]octan-2-one. The Lewis Acid (FeCl3 or BF3•OEt2)-assisted cyclization of the same substrate in air at room temperature afforded aryl(halo)methylenebicyclo[3.2.1]octan-2-one de-rivatives containing a C(sp2)-halo bond (halo = Cl or F).