葉名倉Yeh, Ming-Chang翁于婷Weng, Yu-Ting2019-09-04不公開2019-09-042015http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22G060242081S%22.&%22.id.&http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/100005本論文分為三個部分，分別探討路易士酸（Lewis Acids）及布忍斯特酸（Brønsted Acid）輔佐含氮烯炔醇化合物及烯炔胺化合物進行分子內環化反應。 第一部分以三苯基四氟硼酸鹽（CPh3BF4）輔佐三級烯丙醇的氮-3-芳香基丙炔吡咯啶化合物的環化反應，過程中，三苯基四氟硼酸鹽同時作為路易士酸及氟化試劑。反應在室溫、氮氣下，經碳氟化，生成新的碳（sp2）－氟鍵，得到高立體選擇性的烯氟吡咯啶衍生物。也可以雙三氟甲烷磺醯亞胺（NHTf2）輔佐進行環化，得到酮基吡咯啶衍生物。 第二部分以三氟甲磺酸銦（III）（In(OTf)3）催化雙甲基取代烯炔醯胺化合物。反應在室溫、氮氣下，透過中間體乙烯亞胺的形成，得到高產率的2-胺基茚衍生物。亦可以三溴化銦（III）（InBr3）輔佐雙溴取代烯炔胺化合物，得到三溴甲基取代的2-胺基茚衍生物。 第三部分是以三氟甲磺酸銦（III）（In(OTf)3）催化N-異丁烯基-2-炔醯胺吡咯化合物。反應在室溫、氮氣下，可得到吲衍生物。This thesis is composed of three parts, discussing Lewis- and Brønsted-acid-mediated intramolecular cyclization reactions of N-containing enynols and enynamides. First, CPh3BF4-promoted cyclization of N-3-arylpropargylpyrrolidine-tethered tertiary allylic alcohols under nitrogen at room temperature produced 1-isobutenyl-2-(fluoro(phenyl)methylenylhexahydro-1H-pyrrolizidine) with excellent stereoselectivity. In this reaction, CPh3BF4 reacted as both the Lewis acid andthe fluoride source for carbofluorination, providing new C(sp2)－F bond. In addition, utilizing NHTf2 afforded pyrrolizidine skeleton containing a keto functionality. Second, In(OTf)3-catalyzed cyclization of aromatic ortho-isobutenyl-substituted enynamides under nitrogen at room temperatures afforded 2-aminoindenes. This reaction proceeded via a highly reactive keteniminium intermediate, generated in situ from ynamides and a Lewis acid, providing 2-amino-1H-indenes in high yields. Furthermore, changing the ortho-isobutenyl substitution to the ortho gem-dibromovinyl substitution, the cyclization produced the carbobromination product 1-tribromomethyl-2-amino-1H-indene in the presence of 1.2 eq. of InBr3. Third, In(OTf)3 enabled efficient synthesis of indolizine derivatives from N-isobutenyl-2-ynamidepyrroles.三苯基四氟硼酸鹽烯氟化合物碳氟化雙三氟甲烷磺醯亞胺環化異構化吡咯啶三氟甲磺酸銦炔醯胺化合物乙烯亞胺茚衍生物三溴化銦三溴甲基吲衍生物triphenylcarbenium tetrafluoroboratecarbofluorinationvinyl fluorideindium(III) trifluoromethanesulfonatecyclooisomerizationpyrrolizidineindium(III) trifluoromethanesulfonateynamideketeniminiumindeneindium(III) bromidetribromomethaneindolizine