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第一部份 天然物Axamide-1, Axisonitrile-1與cis-Dracunculifoliol之全合成研究, 第二部份 微波加熱應用於α-碘基酮之自由基環化反應研究
Thesis

第一部份 天然物Axamide-1, Axisonitrile-1與cis-Dracunculifoliol之全合成研究, 第二部份 微波加熱應用於α-碘基酮之自由基環化反應研究

郭原良
Masters, National Tsing Hua University
2007

Abstract

a-碘基酮自由基環化反應天然物全合成微波加熱1,5-氫轉移 axamide-1axisonitrile-1cis-dracunculifoliola-iodoketoneRadical cyclizationmicrowave1,5-hydrigen shift.
There are two parts in this thesis. In the first part we want to mention the racemic total synthesis of axamide-1, axisonitrile-1 and cis-dracunculifoliol. Radical cyclization of 89 furnished the cis-hydrindanone core. Subsequently desilylation of 96 afforded an exo-double bond in the backbone 90. Compound 90 is a potential synthetic intermediate for this class of natural product. This was followed by reduction, mesylation and substitution. After tandem alkylation-reduction of nitrile 91 and the secondary amine was formed. Finally, the synthetic route was accomplished by formylation of the amine and axisonitrile-1 was made by dehydration of compound 1. By the way, we also used compound 90 as a starting material. After Wittig reaction and hydration of 90, then we could made aldehyde 106. It was a pity that 1,2-addition of 106 could not make the cis-dracunculifoliol directly. Therefore, 107 was oxidized and followed by reduction then the desired compound would be achieved.In the second part, the substituted □-iodoketone was applied in microwave heating and proceeds high-speed radical cyclization. Compared to conventional tin-catalyzed procedure, we found significant not only the vinyl-iodo products but also some new result from obviously 1,5-hydrigen shift. In some kinds of examples, we found the cyclization could also possible accomplished in aqueous solution. It is helpful to reduce the damage of earth resulted from organic solvent. Then we also realized that allen-type compounds could cyclized faster than alkynyl-type compounds.

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