環丙基取代之釕金屬亞丙烯基錯合物與芴衍生物取代的新穎金屬錯合物

Chien-Chih Chen; 陳建志

請用此 Handle URI 來引用此文件： http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/33307

完整後設資料紀錄

DC 欄位	值	語言
dc.contributor.advisor	林英智(Ying-Chih Lin)
dc.contributor.author	Chien-Chih Chen	en
dc.contributor.author	陳建志	zh_TW
dc.date.accessioned	2021-06-13T04:33:51Z	-
dc.date.available	2011-08-04
dc.date.copyright	2011-08-04
dc.date.issued	2011
dc.date.submitted	2011-07-27
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dc.identifier.uri	http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/33307	-
dc.description.abstract	釕金屬錯合物和帶有環丙基的丙炔醇化合物，在六氟磷酸鉀存在下，進行反應生成釕金屬環丙基亞丙烯基錯合物2。藉由加熱或鹵鹽加成或鈀催化，錯合物2中的三元環可以擴環，生成帶有五元環的亞乙烯基錯合物4。擴環反應是藉由在連續雙鍵的Cβ碳和環丙基中的亞甲基生成碳碳鍵來進行。推測中間體B和C在鈀催化的反應中扮演了關鍵的角色。在2和吡咯的反應中，兩個碳碳鍵連續生成，而形成6。其中一個是發生在吡咯環的二號碳和2的Cγ碳之間，另一個則是在吡咯的三號碳和Cα碳之間。這個反應是藉由吡咯的加成和1,3-氫原子的移動來進行。我們在不同的溶劑中，進行化合物2與硼氫化鈉的反應生成7和8的混合物。連續雙鍵的氫化具有位置選擇性。使用不同的溶劑會導致7和8有不同的比例。如果在二氯甲烷或氯仿中加入有質子的溶劑，如甲醇，則會增加8的產率，顯示在其中硼氫化反應和去硼化反應的速率都會增加。在含有微量水的氯仿中用氟硼酸來質子化2生成了環狀碳烯錯合物14。在二甲基甲醯胺中對錯合物2進行加熱生成了13，14和15混合物。有趣的是，在含有碘化鈉的二氯甲烷中，當錯合物2和氟硼酸進行反應時，一個不被預期的碳碳雙鍵還原反應發生了。這個反應生成了17而且將17和過量的甲醇鈉進行反應透過了分子內環化過程則生成了亞乙烯基錯合物19。鈀催化錯合物2的開環反應導致了環丙基的開環，生成了新穎的釕金屬鏻炔基錯合物20。然而，鹼促進的鈀催化錯合物2的反應生成了兩種釕金屬炔基錯合物21和23。除此之外，藉由甲醇基的親和性取代反應則21可以從20得到。再者，錯合物25固有的分子內複分解反應生成26而且特別的鈀催化25的碳氫鍵活化生成了27而27也可以藉由24的烯丙基化得到。錯合物2和三乙胺或者是吡啶的反應都導致了環丙基的開環個別生成了陽離子性的釕金屬炔基錯合物28和30。此外，特別的雙陽離子的環狀亞乙烯基錯合物31帶有九元環可以從2和2-乙炔基吡啶在甲醇中的反應得到。整個反應是藉由開環過程和9-endo-dig的環化模式。釕金屬錯合物和32，在六氟磷酸鉀存在下，進行反應生成了兩種錯合物33和34。此外錯合物36，38和也可以由類似的方法得到。釕金屬錯合物和41在甲醇中進行反應生成了錯合物42在二氯甲烷中則生成了43。將45去質子化則生成了炔基錯合物46。用烯丙基碘將錯合物46烷基化則生成了錯合物47。再者，將47去質子化則產生了炔基錯合物48並伴隨著51的離去。同樣地，錯合物52和53也可以用相同的方法合成。對烯基上帶有一個甲基的化合物54來說，在C	zh_TW
dc.description.abstract	The cyclopropyl allenylidene complex [Ru]=C=C=C(R)(C3H5) ([Ru] = Cp(PPh3)2Ru, 2, R = thiophene) is prepared from the reaction of [Ru]Cl with cyclopropyl propargyl alcohol 1 in the presence of KPF6. Thermal treatment, halide anion addition, and Pd-catalyzed reactions of 2 all lead to a ring expansion of the cyclopropyl group giving the vinylidene complex 4 with a five-membered ring. This ring expansion proceeds via a C-C bond formation between C	en
dc.description.provenance	Made available in DSpace on 2021-06-13T04:33:51Z (GMT). No. of bitstreams: 1 ntu-100-F95223037-1.pdf: 6396988 bytes, checksum: 606c7a6d566d44ab6b864f209572d224 (MD5) Previous issue date: 2011	en
dc.description.tableofcontents	Contents I Abstract IV Abstract in Chinese VII Numbering and Structure of Compounds X Graphical Abstract XIX Part I. Reactions of Cp Phosphine Ruthenium Allenylidene Complex Tethering a Cyclopropyl Group 1 Abstract 2 Introduction 3 Results and Discussion 6 Ring Expansion of Cyclopropyl Group on Allenylidene. 6 Thermal Ring Expansion. 7 Halide-Assisted Ring Expansion. 9 Ring Expansion by Pd Catalyst. 10 Cyclization with Pyrrole. 13 Hydrogenation of Allenylidene. 17 Conclusions 22 Experimental Section 23 References 33 Part II. New Carbyne Chemistry from Cp Phosphine Ruthenium Allenylidene Complex Tethering a Cyclopropyl Group 39 Abstract 40 Introduction 42 Results and Discussion 44 Synthesis of Specific Seven-Membered Cyclic Alkoxy Carbene Complex 14. 44 Seven-Membered Ring vs Five-Membered Ring. 45 Synthesis of Ring-Opening Vinyl Acetylide Complex 16. 46 Transformations of Complexes 13-15 to Complex 16. 47 Synthesis of Complex 19 from 2 Accompanied with “H2” Addition. 48 Conclusions 52 Experimental Section 54 References 61 Part III. Pd-catalyzed C-C Bond and C-H Bond Activation Reactions of Cp Phosphine Ruthenium Complexes Tethering a Cyclopropyl Group 64 Abstract 65 Introduction 66 Results and Discussion 68 Palladium-Catalyzed Ring Opening Reaction. 68 Bases Promoted Palladium-Catalyzed Ring Opening Reaction. 72 Metathesis Reaction of 25. 75 Allylation and C-H Bond Activation. 77 Conclusions 80 Experimental Section 81 References 88 Part IV. Ring-opening reactions of Cp Phosphine Ruthenium Allenylidene Complex Tethering a Cyclopropyl Group with Other Nucleophiles 91 Abstract 92 Introduction 93 Results and Discussion 95 Reactions with Amines. 95 Reaction with Pyridine. 97 Synthesis of Specific Nine-Membered Cyclic Dicationic Vinylidene Complex 31 98 Conclusions 101 Experimental Section 102 References 105 Part V. Reactions of Ruthenium Complexes from Fluorene Derivatives 107 Abstract 108 Introduction 110 Results and Discussion 112 Intramolecular Cyclization and Dehydration Reactions. 112 Cyclization Reactions of Fluorene Derivatives. 114 Reactions of 41 with a Propargylallylether Group. 117 Reactions of Propargylic Fluorene 44. 118 Reactions of 54 with a Methyl Substituent. 122 Reactions of 61 with No Methyl Group on the Olefinic Part. 124 Conclusions 127 Experimental Section 129 References 148 Appendix A. X-Ray Crystallographic Data 152 Appendix B. NMR Spectra Data 190
dc.language.iso	en
dc.title	環丙基取代之釕金屬亞丙烯基錯合物與芴衍生物取代的新穎金屬錯合物	zh_TW
dc.title	Ruthenium Allenylidene Complex Tethering a Cyclopropyl Group and Novel Complexes from Fluorene Derivatives	en
dc.type	Thesis
dc.date.schoolyear	99-2
dc.description.degree	博士
dc.contributor.oralexamcommittee	劉緒宗(Shiuh-Tzung Liu),劉瑞雄(Rai-Shung Liu),葉名倉(Ming-Chang Yeh),王朝諺(Tiow-Gan Ong)
dc.subject.keyword	亞丙烯基,釕金屬,擴環,開環,異構化,環化,環丙基丙二烯,碳炔,烷氧基碳烯,鈀催化反應,[2+2] 反應,碳碳鍵活化,碳氫鍵活化,雙陽離子環狀亞乙烯基,9-endo-dig反應,芴,	zh_TW
dc.subject.keyword	allenylidene,ruthenium,ring expansion,ring opening,isomerization,cyclization,cyclopropyl allene,carbyne,alkoxy carbene,Pd-catalyzed reactions,[2+2] reaction,C-C bond activation,C-H bond activation,dicationic cyclic vinylidene,9-endo-dig reaction,fluorene,	en
dc.relation.page	219
dc.rights.note	有償授權
dc.date.accepted	2011-07-27
dc.contributor.author-college	理學院	zh_TW
dc.contributor.author-dept	化學研究所	zh_TW
顯示於系所單位：	化學系

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