博士 / 國立臺灣師範大學 / 化學系 / 100 / This dissertation contains three topics. The first part is the synthesis of cyclopenta[b]indoles via the palladium(II)-catalyzed cascade reaction of alkynylanilines bearing a tethered cyclic enones. The second part is the synthesis of 7-azaspiro[4.5]decanes or spiro[4.4]nonanes via the TfOH-catalyz-
ed tandem semipinacol rearrangement, followed by alkyne-aldehyde metathesis. Finally, the synthesis of the C-2 epimer of kainoic acid is described.
(1) The Pd(II)-catalyzed tandem intramolecular cyclization reaction of alkynylanilines bearing a tethered cyclic enones afforded the cyclopenta[b]indole derivatives. Firstly, the Pd(II) catalyst coordinated to alkyne to form a Pd-alkyne complex. Then attack of the tosylamide onto the Pd-alkyne moiety took place to give a palladiated indole. The resulting arylpalladium underwent an intramolecular Michael addition to the pendant conjugate enones to provide the cyclopenta[b]indole derivatives. Both the catalyst PdCl2(PhCN)2 and the solvent DMF are critical for the reaction.
(2) A TfOH-catalyzed tandem reaction of 2,3-epoxy-5-aza-5-tosyl-7-yn-8-
aryl-1-ols is reported. The reaction undergoes a tandem semipinacol rearrangement/alkyne-aldehyde metathesis to afford azaspirocyclic or spirocyclic derivatives. The C-2 arylpropargylsulfonamide-tethered 2,3-epoxy-
cyclohexan-1-ones react with Lewis acid, such as FeCl3 or PPh3AuCl/AgOTf to produce 8H-hydroisoquinolines. Substrates bearing a geminal dimethyl group at C-5 and methyl group at C-3 of the ring can be utilized to afford pyrrole or furan derivatives using a catalytic amount of Lewis acid.
(3) PPh3AuCl/AgOTf catalyzed intramolecular Claisen rearrangement of (Z)-enynol was developed to provide cis-3-acyl-4-alkenylpyrrolidines containing an oxazoline ring, which are the precursor of the C-2 epimers of kainoic acids.
| Identifer | oai:union.ndltd.org:TW/100NTNU5065109 |
| Date | January 2011 |
| Creators | Ming-Nan Lin, 林明楠 |
| Contributors | Ming-Chang Yeh, 葉名倉 |
| Source Sets | National Digital Library of Theses and Dissertations in Taiwan |
| Language | zh-TW |
| Detected Language | English |
| Type | 學位論文 ; thesis |
| Format | 741 |
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