臺灣博碩士論文加值系統

利用釕金屬錯合物(RuCp(PPh3)2Cl)為起始物，與有機物配基1a以及鹽類NH4PF6，在二氯甲烷溶液中反應，可得釕金屬錯合物3。假若將有機物1a在三鍵附近延伸一個碳形成有機物2，在同樣條件，可進行分子內環合反應。針對釕金屬錯合物3的化學性質，我們提供不同的親核基團與之進行反應，例如NaBH4、砒硌和格里納試劑，可形成相對應的釕金屬錯合物(5,6,8,10a-b)。另一方面，在釕金屬錯合物3末端所修飾的環丙烷基，可經由三級氨引誘開環，我們如果把NEt3 加入反應，可得到中性釕金屬乙炔基錯合物12a。有趣的是，在一級氨propargyl amine以及甲醇的存在下，釕金屬錯合物3可形成錯合物17a。同時，我們也發現鹵素可擔任開環的角色，環打開後，分子內隨即進行烷基化反應，產生碳-碳鍵，擴大成五環。從文獻中得知，類似3的錯合物在遇到強酸的情況下，可生成卡拜錯合物，我們也發現到在四氟硼酸的作用下，氯仿中所含的水可攻擊三環使之開環，再由氧原子攻打在最靠近金屬碳上形成七環。
在合成釕金屬錯合物3的時候，我們也發現到，如將溶液改為氯仿或是水，其他條件不變，則可以進行催化反應。提高溫度至55℃，可得到較佳的產率，值得注意的是，這個催化反應對於產物的順反異構物，具有完全的選擇性。

The allenylidene complex 3 was prepared by the treatment of a CH2Cl¬¬¬¬2 solution of Cp(PPh3)2RuCl with 1-cyclopropyl-1-phenylprop-2-yn-1-ol, 1a in the presence of NH4PF6. The reaction of 2 with Cp(PPh3)2RuCl and NH4PF6 in CH2Cl2 proceeded via an intramolecular cyclization to afford the carbene complex 4. Reactions of 3 with a variety of nucleophiles, like NaBH4 and pyrrole formed 5, 6 and 8 respectively. Besides, Grignard reagents could attack on C¬γ of 3 to acquire the neutral acetylide complexes 10a-b. Complexes 10a-b underwent protonation reactions affording the corresponding vinylidene complexes 11a-b. When the allenylidene complex 3 was dissolved in CH2Cl¬2 or CHCl3 in the presence of amine, ring-opening of the cyclopropane group occurred. For instances, a CH2Cl2 solution of 3 was treated with triethylamine, and the acetylide complex 12a was obtained. It is noteworthy that the reaction of 3 with propargyl amine in the presence of methanol proceeds via a retro-ene process to give 17a. Furthermore, iodide could attack the cyclopropyl group of 3, which was followed by a subsequent C-C bond formation with the halides serving as a leaving group to yield complex 15. Complex 3 could also react with acid to yield a carbyne intermediate, and then water could act as a nucleophile to induce ring opening to give the final carbene product 16. The reaction of 18a with Cp(PPh3)2RuCl leads to the formation of 19a. The cyclization may proceed via an allenylidene intermediate which was not observed in this system. Interestingly, treatment of 1a with water in the presence of catalytic amount of ruthenium chloride complex Cp(PPh3)RuCl afforded (E)-1,3-enynes 21a with high selectivity.

Contents
Contents I
Numbering and Structure of Compounds III
Reaction Scheme VI
Abstract 1
中文摘要 3


Part I Reaction of Ruthenium allenylidene complex containing a cyclopropyl group 4 Introduction 5
Results and Discussion 7
Conclusions 29
Experimental Section 30
References 52
Appendix I : X-ray Crystallographic Data 58
Appendix II : Spectra Data of Part I 67

Part II Ring opening reaction catalyzed by ruthenium
chloride 129
Introduction 130
Results and Discussion 131
Enyne compounds catalyzed by [Ru]Cl. 131
Conclusions 134
Experimental Section 135
References 137
Appendix III : Spectra Data of Part II 138

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