| Summary: | 博士 === 國立清華大學 === 化學系 === 88 === The thesis consists of three parts. The first part describes intramolecular 1,5-hydrogen atom transfer from , and carbons of cycloalkanones to alkenyl or phenyl radicals on the side chain was systematically studied. Deuterium labeling technique combined with some theoretical calculation conformed that the observed hydrogen atom transfer is mostly controlled by the conformational factors.
The second part is about total synthesis of dimethyl gloioiphone A. Thus, alkylation of the anion of dimethylhydrozone of cyclopentanone with 5-iodopent-1-yn followed by hydrosis gave keton 12. Iodination then radical spiro cyclization gave spiro ketone 25. After several steps of functional group transfer, the total synthesis of dimethyl gloioiphone A was achieved.
The final part describes synthesis of ingenol. The out,out-tricyclo[7.4.1.01,5]tetradecan-14-one was achieved by using -carbonyl radical spirocyclization and ring-closing olefin metathesis as key steps.
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