一、含氮雙烯炔分子內Diels-Alder環化反應：六氫苯[cd]吲哚的合成 二、三氟化硼輔佐3-(5-芳香基-4-戊炔基)環己-2-烯-1-矽醚分子內環化反應：含氟螺旋[4.5]癸烯衍生物的合成

Abstract

本論文共分為三個主題，第一部分，利用分子內Diels-Alder反應合成吲哚衍生物，以1-甲苯磺醯炔丙胺基-3-乙烯基環己-2-烯作為起始物，於加熱條件下進行Diels-Alder環化反應，再行氧化反應得到六氫苯[cd]吲哚化合物。第二部分，以三氟化硼做為路易士酸及氟離子來源，輔佐3-(5-芳香基-4-戊炔基)環己-2-烯-1-矽醚，進行分子內環化反應，同時生成碳（sp2）－氟單鍵，合成含氟螺旋[4.5]癸烯衍生物。最後以金（I）和銀共催化3-(N,3-二苯丙炔醯胺基)環己-2-烯-1-酮，進行6-endo-dig分子內環化反應，合成二氫喹啉酮衍生物。This study covers three separated topics. The first work is the synthesis of hexahydrobenzo[cd]indoles via intramolecular Diels-Alder reaction from 1-tosylpropargylamino-3-vinylcyclohex-2-enes. The reaction proceeded via [4+2] cycloaddition followed by oxidation to generate hexahydrobenzo[cd]- indoles. The second part of the thesis is the synthesis of fluorinated spiro[4.5]- decenes from tert-butyldimethyl-silyl-protected 3-(5-arylpent-4-yn-1-yl)cyclo- hex-2-en-1-ols using BF3•OEt2. In this reaction, BF3 reacted as both the Lewis acid and the fluoride source for cyclization/fluorination. The method provided an easy access to spirocyclic skeletons with concomitant formation of a C(sp2)−F bond. Finally, the gold(I)-catalyzed intramolecular cycloisomeri- zation of the 3-(N,3-diphenylpropiolamido)cyclohex-2-en-1-one proceeded through a cationic gold intermediate to afford a dihydroquinolinone. The reaction underwent an endo-dig cyclization to generate an iminium intermedi- ate followed by deprotonation/protodeauration to give a dihydroquinolinone and regenerate the Au(I) catalyst into the catalytic cycle.