此論文研究是首度以有機磷氧化物為自由基來源搭配醇類溶劑對乙烯芳香環 (vinylarene) 衍生物進行的不對稱1,2烷氧基磷氧基化反應，在五價手性氧釩催化劑搭配氧化劑TBHP的系統下完成。在此系統中，有機磷氧自由基加成至乙烯芳香環衍生物後，形成的碳中心自由基能藉由結構中的磷氧雙鍵配位於手性氧釩金屬錯合物的軸向，增進自由基中心手性環境的辨認進而達到高度的鏡像選擇性。
本反應以溫和的條件及官能基共適性為特色，十種不同的醇類可以成功地進行醚化 (etherification) 反應；以甲醇為溶劑，三十九種不同的乙烯芳香環衍生物能順利的進行1,2烷氧基磷氧基化反應，並多數保持在70%以上的產率、80%以上的鏡像選擇性。(R)組態的產物結構藉由X光繞射分析 (X-ray crystallographic analysis) 數個再結晶產物得到確認。將有機磷氧化物改以苯亞磺酸或苯甲醛作為自由基來源也可得到對應的1,2氧烷基磺醯基化及1,2氧烷基醯基化產物，鏡像選擇性表現與中間體配位能力呈正相關，驗證了自由基中間體對氧釩金屬配位的重要性。

The current thesis covers the first 1,2-alkoxylphosphinoylation of vinylarene derivatives catalyzed by chiral oxovanadium species with diphenylphosphine oxide in the presence of TBHP in a given alcohol was established. In these reactions, the carbon-centered radical intermediate generated from addition of diphenylphosphinoyl radical to vinylarene can coordinate to axial position of the chiral oxovanadium anti to V=O unit by phoshphinoyl group, which strongly enhanced differentiation of chiral environment, and thus achieving higher enantioselectivity.
These catalytic reactions feature very mild reaction conditions and high functional group compatibility. Styrene can smoothly undergo 1,2-alkoxylphosphinoylation over 10 different alcohols; 39 different kind of vinylarene species can smoothly undergo 1,2-methoxylphosphinoylation when MeOH was employed as solvent. In most cases, over 70% yield and 80% enantiomeric excess can be obtained. (R)-configuration was confirmed by X-ray crystallographic analysis of several recrystallized products. Replacing radical source from phosphine oxide to sulfinic acid or benzaldehyde can also obtain 1,2-methoxysulfonylation and 1,2-methoxyacylation products, and the results show positive correlation between enantioselectivity and coordination ability, which emphasized the importance of coordination between carbon-centered radical intermediate and chiral oxovanadium.

中文摘要...............................................I
Abstract..............................................II
目錄..................................................III
式目錄................................................V
圖目錄................................................VII
表目錄................................................VIII
縮寫對照表............................................IX
第一章、緒論..........................................1
第一節、烯類雙官能基化反應...........................1
1. 氧化磷及磷酸酯自由基的雙官能基化反應 (外消旋).....3
2. 氧化磷及磷酸酯自由基的雙官能基化反應 (手性).......11
3. 1,2-官能基磷氧基化反應目前的發展與困境...........14
第二節、氧釩錯合物的雙官能基化反應....................18
第三節、研究動機....................................22
第二章、結果與討論....................................25
第一節、初始反應探討................................25
第二節、催化劑模板的最佳化..........................28
第三節、醇類溶劑通用性檢測及最佳化...................33
第四節、共溶劑檢視..................................37
第五節、反應溫度的最佳化............................40
第六節、不同苯乙烯衍生物的通用性檢測.................41
1.單取代苯乙烯效應...............................41
2.雙取代苯乙烯及雜環效應..........................45
第七節、磷酸酯作為自由基來源的測試...................50
第八節、苯亞磺酸與苯甲醛作為自由基來源的測試..........51
第九節、反應機制...................................52
第十節、鏡像選擇性的探討............................54
第十一節、結論.....................................56
第三章、分析儀器實驗步驟及光譜數據.....................57
第一節、分析儀器...................................57
第二節、實驗步驟及光譜數據..........................59
1.催化劑3f的合成................................59
2.初始反應探討的合成.............................61
3.最佳化及通用性檢測相關的合成....................63
參考文獻............................................107
附錄壹、核磁共振光譜圖...............................S1
附錄貳、X-ray 單晶繞射結構解析數據....................S66

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