酸輔佐烯炔醇-和烯炔醯胺-化合物的分子內環化反應－吡咯啶、茚和吲衍生物的合成
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2015
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Abstract
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.
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.
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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 tetrafluoroborate, carbofluorination, vinyl fluoride, indium(III) trifluoromethanesulfonate, cyclooisomerization, pyrrolizidine, indium(III) trifluoromethanesulfonate, ynamide, keteniminium, indene, indium(III) bromide, tribromomethane, indolizine