本論文主要在探討□-羰基自由基螺旋環化反應及其在天然物全合成之應用，全文共分為三部分。第一部分以氘化三丁基錫(Bu3SnD)為試劑，來研究□-碘基酮化合物在進行自由基環化反應的過程所進行的1,5-氫原子轉移現象。由理論計算與實驗的結果顯示﹕碘基酮化物41、53、88及89在進行自由基環化反應的過程會進一步進行1,5-氫原子轉移的反應，而在進行1,5-氫原子轉移反應時，分子構形的因素對此反應的影響會較自由基穩定度的因素更為重要。
第二部分是有關於dimethyl gloiosiphone A的全合成研究。本文利用□-碘基酮22的自由基螺旋環化反應為關鍵步驟來獲得spiro[4.4]nonane的螺旋骨架25後，再經由碘化及氧化反應得到化合物47，將47進行甲基化反應接著與甲氧鈉進行置換反應，可得到二甲氧基烯酮化合物51，最後進行烯丙位氧化反應、二羥化反應以及甲基化反應後成功的完成dimethyl gloisoiphone A (2)全合成研究。

第三部分在探討天然物ingenol的合成研究。相同的以□-羰基自由基螺旋環化反應為關鍵性步驟，利用□-碘基酮化合物43建立ingenane的A、C環42之後，再經由烷化反應以及Grubbs所發展的釕金屬催化劑50進行合環歧化反應，順利獲得具有outside-outside ingenane結構的化合物72。

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 l ling 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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