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研究生:李政遠
研究生(外文):Cheng-Yuan Lee
論文名稱:釕金屬錯合物誘發含環戊烷及炔基化合物反應之研究
論文名稱(外文):Study on Reactions of Alkynyl Compounds Containing Cyclopentyl Group Induced by Ruthenium Complexes
指導教授:林英智林英智引用關係
指導教授(外文):Ying-Chih Lin
口試委員:劉陵崗詹益慈
口試委員(外文):Ling-Kang LiuYi-Tsu Chan
口試日期:2014-06-25
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:2014
畢業學年度:102
語文別:英文
論文頁數:128
中文關鍵詞:釕金屬乙炔基亞乙烯基碳烯環戊烷開環反應重排反應縮環反應環化反應
外文關鍵詞:rutheniumacetylidevinylidenecarbenecyclopentaneoxiranering-openingrearrangementring-contractioncyclization
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Abstract
Treatment of propargyl alcohol 1 with [Ru]-Cl ([Ru] = CpRu(PPh3)2) in the presence of KPF6 and K2CO3 in CH2Cl2 affords the acetylide complex 2. The dehydration takes place at CδH and CγOH, instead of at CβH and CγOH. Then, protonation of 2 with HBF4 in ether produces the vinylidene complex 3. Formation of 1,3-enyne 5 directly from 1 is catalyzed by 30 mol % of [Ru]NCMe+PF6- in MeOH at 60oC or indirectly from 3 by stirring the solution in CH3CN/CHCl3 for 12 h. Alkylation of 2 by allyl bromide as an alkylation reagent results in formation of vinylidene complex 4. Intramolecular cyclization of 6a and 6b each containing a hydroxyl group with [Ru]-Cl in the presence of NH4PF6 in CH2Cl2 for 12 h afford oxacyclic carbene complexes 7a and 7b, respectively. However, treatment of 6a and 6b with 10 mol% of [Ru]-Cl in n-BuNH2 at 90oC for 12 h affords the dihydrofuran and dihydropyran products 8a and 8b, respectively.
Epoxidation reaction adds an oxygen atom across the double bond of 5 to yield 1-alkynyloxirane 9. Reaction of 9 with [Ru]-Cl in the presence of KPF6 in MeOH affords the spiro-oxacyclic carbene complex 10. Rearrangement of 9 with a Lewis acid, BF3‧Et2O, affords α-alkynylketone 11 via a ring-expansion process of the cyclopentyl group. Treatment of 11 with [Ru]-Cl in different alcohols in the presence of KPF6 at room temperature affords the fused oxabicyclic carbene complex 12 via intramolecular cyclization reaction. However, in the presence of NH4PF6 in CH2Cl2, the same reaction affords 10 via cascade cyclization/ring-contraction.
When 1,6-enyne 14a is treated with 1 mole equiv. of [Ru]-Cl in the presence of NH4PF6 in CH2Cl2 at room temperature for 24 h, complex 15, the six-membered oxacyclic product 16a, and an aldehyde molecule 17 in a ratio of 1:2:1 are isolated. However, in the presence of KF in MeOH for 12 h, instead of NH4PF6 in CH2Cl2, only 2 is obtained. Three analogous compounds 14b, 14c, and 14d are prepared similarly, using different ketones as staring materials. Furthermore, the reaction of 14a-14d with 20 mol% of [Ru]-Cl in the presence of NH4PF6 in CH2Cl2 at 40oC for 12 h affords six-membered oxacyclic 16a-16d in better yield. In addition, structures of complexes 7a, 10 and 12a’ are confirmed by X-ray diffraction analysis.

Contents I
Numbering and Structure of Compounds II
Reaction Scheme V
Abstract 1
Abstract in Chinese 3
Introduction 4
Results and Discussion 10
Formation of Acetylide Complex 2 10
Protonation and Alkylation of Acetylide Complex 2 12
Formation of 1,3-Enyne Compound 5 13
Formation of the Oxacyclic Carbene Complex 7 15
Formation of the Dihydrofuran and Dihydropyran Derivatives 18
Ring-Opening of Epoxide Compound 9 20
Meinwald Rearrangement Using Lewis Acid 23
Formation of the Fused Oxabicyclic Carbene Complex 12 24
Formation of the Acetylide Complex 13 29
Cyclization Reaction of 1, 6-Enyne 14 31
Conclusions 40
Experimental Section 42
References 66
Appendix I: X-Ray Crystallography Data 72
Appendix II: NMR Spectra Data 98


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