1. Intramolecular Diels-Alder Reactions of Azadienynes: Synthesis of Hexahydrobenzo[cd]indoles 2. BF3-Assisted Synthesis of Fluorinated Carbospirocycles from TBS-Protected 3-(5-Arylpent-4-yn-1-yl)cyclohex-2-en-1-ols

• Main Authors: Hsiao-Ju Hsu, 徐筱茹
• Other Authors: Ming-Chang P. Yeh
• Format: Others
• Language: zh-TW
• Published: 2013
• Online Access: http://ndltd.ncl.edu.tw/handle/73344075993909987522

碩士 === 國立臺灣師範大學 === 化學系 === 101 === 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.