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研究生:馬浩瑋
研究生(外文):Hao-Wei Ma
論文名稱:在釕金屬上鄰位-3-(5-烯-1-已炔)酚的分子內環化及其相關反應之研究
論文名稱(外文):The intramolecular Cyclization of o-(hex-5-en-1-yn-3-yl)phenols and Related Reactions on Ruthenium
指導教授:林英智林英智引用關係
指導教授(外文):Ying-Chih Lin
學位類別:碩士
校院名稱:國立臺灣大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2010
畢業學年度:98
語文別:英文
論文頁數:171
中文關鍵詞:烯炔金屬碳烯基環化色滿
外文關鍵詞:Enynerutheniumoxocarbenecyclizationchromane ring
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The intramolecular cyclization of 1,5-enyne mediated by CpRu(PPh3)2Cl leading to the formation of chromane ring derivatives is described. For the enyne compound 2a-2c with different substitution on the aromatic ring, the reaction takes place at the propargylic alcohol first giving the vinylidene intermediate which could undergo an intramolecular cyclization to yield the cyclic oxocarbene complexes (5a-c and 5a’ and 5c’). Moreover, the cyclization may proceed via a vinylidene intermediate which was not observed in our system. Modifications of various substituents at Cb by the use of different alkyl halides can be readily achieved in mild condition. For the chromane ring derivatives 9, the two allyl groups underwent ring closing metathesis reaction in the presence of Grubb’s catalyst and yielded the tricyclic product 10. Additionally, photolysis of 7, 8 or 9 results in dissociation of a PPh3 ligand from the metal center which is accompanied with filling in the vacant site by the counter anion, iodide, to form neutral complexes 11, 12 or 13. Besides, both substituents at Cb and oxygen-free aromatic ring of the chromane moiety participate well, with reaction time and product selectivity as a function of the steric and electronic character. These chemical reactions and their mechanism are corroborated by structure determinations of three ruthenium complexes using single crystal X-ray diffraction analysis.

Content I
Numbering and Structure of Compounds III
Reaction Scheme V
Part I Ruthenium Cyclic Oxocarbene Complexes from o-(hex-5-en-1-yn-e-yl)phenol 1
中文摘要 2
Abstract 3
Introduction 4
Results and Discussion 6
Formation of Cyclic Carben Complexes. 6
Intramolecular ring closing metathesis of 9. 11
Photolysis of the cyclic carbene complex 5. 12
Conclusions 17
Experimental Section 18
References 36
Appendix I: X-Ray Crystallographic Data 41
Appendix II: Spectra Data of Part I 56
Part II The Intramolecular Cyclization of 1,7- and 1,8-enynes on Ruthenium 132
中文摘要 133
Abstract 134
Introduction 135
Results and Discussion 136
Reactions of Enynes with Methyl Substituents 136
Conclusions 139
Experimental Section 140
References 144
Appendix III: Spectra Data of Part II 146

Part I
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Part II
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