(一) 路易士酸輔佐矽保護的2-(3-芳香基丙炔基甲苯磺醯胺基)甲基環己-2-烯-1-醇分子內環化反應—異喹啉衍生物的合成 (二) 布忍斯特酸輔佐1-(3-芳香基丙炔基)-2-甲醛吡咯啶炔醛置換反應—吡口巾衍生物的合成

Abstract

本文分別探討路易士酸（Lewis Acids）輔佐含氮烯炔醇化合物及布忍斯特酸（Brønsted Acids）輔佐含氮炔醛化合物，進行分子內環化反應。本文主要分三部份進行探討：第一部份以三氯化鐵作為路易士酸和氯離子來源，輔佐第三丁基二甲基矽保護的2-(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，空氣下，進行分子內環化，合成含氯八氫異喹啉衍生物。第二部份則以三氟化硼為路易士酸、乙腈為溶劑，進行第三丁基二甲基矽保護之2-(3-芳香基丙炔基甲苯磺醯胺基)甲基環己-2-烯-1-醇化合物環化反應，在室溫，空氣下，合成八氫異喹啉為主架構之醯胺衍生物。第三部份以布忍斯特酸（雙三氟甲基磺醯亞胺）輔佐1-(3-芳香基丙炔基)-2-甲醛-吡咯啶化合物，於高溫，氮氣下，經炔-醛置換反應（Alkyne-Aldehyde Metathesis），生成四氫-1H-吡衍生物。此四氫-1H-吡衍生物於空氣下，逐漸氧化成具芳香性的二氫-1H-吡衍生物。This thesis focuses on acid-promoted intramolecular cyclization of N-containing O-silyl-protected enynols and N-containing ynals. Three major reactions are discussed. First, FeCl3-promoted cyclization of O-silyl-protected 2-(3-arylpropargyltosylamino)methylcyclohex-2-en-1-ols in the air at room temperature produced isoquinoline derivatives containing an aryl(chloro)methylene moiety. In this process, FeCl3 acts as both the activating group and the chloride source. Second, BF3-promoted intramolecular cyclization of O-silyl-protected 2-(3-arylpropargyltosylamino)methylcyclohex- 2-en-1-ols in CH3CN at room temperature in the air provided octahydroisoquinolines having an amide moiety. Third, NHTf2-assisted alkyne-aldehyde metathesis of 1-(3-phenylprop-2-yn-1-yl)-2-formyl- pyrrolidine afforded tetrahydropyrrolizines at 80 ℃ under an atmosphere of nitrogen. The 2,3,5,7a-tetrahydro-1H-pyrrolizines gradually aromatized to 2,3-dihydro-1H-pyrrolizines in the air at ambient temperature.