本文主要探討在有水的條件下，分別以銠卟啉和鈷卟啉絡合物與無張酮反應發生選擇羰基碳及α碳(C(CO)-C(α))鍵活化（下稱碳碳鍵活化）的反應活性和反應機。 / 在200°C，無張芳香和脂肪酮與5, 10, 15, 20-(四甲苯) 銠卟啉絡合物（RhIII(ttp)X，X = Cl 和Me）進反應，生成相對應的碳碳鍵活化產物－銠卟啉酰基絡合物，產最高可達97%。與甲基和乙基酮衍生物相比，丙基酮衍生物有較高的活性,而且丙基酮衍生物的碳碳鍵活化反應甚至能在50°C 的低溫條件下進。 / 根據化學計學，環酮的碳碳鍵開環反應顯示RhIII(ttp)OH 是斷開C(CO)-C(α)鍵的中間體。 / 進一步的反應機研究表明， RhIII(ttp)OH 的羥基是從水中得。RhIII(ttp)X首先進α碳氫鍵活化生成動學產物。經過水解，α碳氫鍵活化產物可以重新形成RhIII(ttp)OH。然後，RhIII(ttp)OH 繼續進碳碳鍵活。 / 另外，經濟的5, 10, 15, 20-(四甲苯) 鈷卟啉絡合物與丙基酮衍生物反應，在室溫下可選擇性進碳碳鍵活化並得到鈷卟啉酰基化合物，產最高達82%。根據化學計學，CoIII(ttp)OH 被認為是碳碳鍵活化的中間體。CoIII(ttp)OH很有可能是通過鈷卟啉與水的歧化反應生成的。 / This thesis focuses on the reactivities and mechanistic studies of the rhodium and cobalt porphyrins (M(por)X) assisted selective carbon(CO)-carbon(α) bond activation (CCA) of unstrained ketones with water. / Unstrained aromatic and aliphatic ketones reacted with 5,10,15,20-tetratolylporphyrinato rhodium(III) complexes, Rh[superscript III](ttp)X (X = Cl and Me), at 200°C to give the corresponding rhodium porphyrin acyls as the CCA products up to 97% yield. Isopropyl ketones exhibit much higher reactivities over methyl and ethyl ketones and the CCA can even occur at a low temperature of 50 °C. / The ring openmg CCA of cyclic ketones suggests the carbon(CO)-carbon(α)bond is cleaved by Rh(ttp )OH according to the reaction stoichiometry. / Further mechanistic investigations suggest that water is the source of hydroxyl group to form Rh[superscript III](ttp)OH. Rh[superscript III](ttp)X first undergoes α-carbon-hydrogen bond activation (α-CHA) to give a kinetic product. Hydrolysis of the α-CHA complex affords Rh[superscript III](ttp)OH for subsequent CCA process. / Alternatively, the economically attractive 5,1 0,15,20-tetratolylporphyrinato cobalt(II) complexes, Co[superscript II](ttp), reacted chemoselectively with isopropyl ketones at the carbon(CO)-carbon(α) bond under room temperature to give high yields of cobalt porphyrin acyls up to 82% yields. Co[superscript III](ttp)OH is identified to be the CCA intermediate as suggested by the reaction stoichiometry. Generation of Co[superscript III](ttp )OH from Co[superscript II](ttp) via the disproportionation with water is proposed. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Fung, Hong Sang. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Abstract --- p.i / Acknowledgements --- p.iv / Table of Contents --- p.v / Abbreviations --- p.ix / Structural Abbreviations for Porphyrins --- p.x / Chapter Chapter 1 --- General Introduction --- p.1 / Chapter 1.1 --- General Introduction to Carbon-Carbon Bond Cleavage --- p.1 / Chapter 1.1.1 --- Organic Examples of Carbon-Carbon Bond Cleavage --- p.1 / Chapter 1.1.2 --- Carbon-Carbon Bond Activation with Transition Metal 2Complexes --- p.2 / Chapter 1.1.2.1 --- Ring Strain Relief --- p.2 / Chapter 1.1.2.2 --- Chelation Assistance --- p.3 / Chapter 1.1.2.3 --- Aromatization --- p.3 / Chapter 1.1.2.4 --- Carbonyl Functionality --- p.4 / Chapter 1.1.2.5 --- β-Alkyl Elimination --- p.4 / Chapter 1.1.2.6 --- Formal Alkane Metathesis --- p.5 / Chapter 1.2 --- Carbon-Carbon Bond Cleavage of Ketones --- p.6 / Chapter 1.2.1 --- Properties of Ketones --- p.6 / Chapter 1.2.2 --- Organic Examples of Carbon-Carbon Bond Cleavage of Ketones --- p.7 / Chapter 1.2.2.1 --- Haloform Reaction --- p.8 / Chapter 1.2.2.2 --- Haller-Bauer Reaction --- p.8 / Chapter 1.2.2.3 --- Baeyer-Villiger & Dakin Oxidation --- p.9 / Chapter 1.2.2.4 --- Beckmann & Schmidt Rearrangement --- p.10 / Chapter 1.2.2.5 --- Favorskii Rearrangement --- p.11 / Chapter 1.2.2.6 --- Norrish Type I Reaction --- p.12 / Chapter 1.2.2.7 --- Hydrolysis with Water --- p.12 / Chapter 1.2.3 --- Carbon(CO)-Carbon(α) Bond Activation of Ketones with Transition Metal Complexes --- p.13 / Chapter 1.2.3.1 --- Stoichiometric C(CO)-C(α) Bond Activation of Ketones --- p.18 / Chapter 1.2.3.1.1 --- Metal Insertion into Strained Ring --- p.18 / Chapter 1.2.3.1.2 --- Decarbonylation --- p.19 / Chapter 1.2.3.1.3 --- Chelation Assisted CCA of Unstrained Ketones --- p.19 / Chapter 1.2.3.1.4 --- Reaction with Benzyne Complex --- p.20 / Chapter 1.2.3.1.5 --- Reaction with Metal Hydroxide --- p.21 / Chapter 1.2.3.2 --- Catalytic C(CO)-C(α) Bond Activation of Ketones --- p.22 / Chapter 1.2.3.2.1 --- Decarbonylation --- p.22 / Chapter 1.2.3.2.2 --- Insertion with Unsaturated Compounds --- p.23 / Chapter 1.2.3.2.3 --- Hydrogenolysis --- p.24 / Chapter 1.2.3.2.4 --- Ring Fusion --- p.25 / Chapter 1.3.3.2.5 --- [4+2+2] Annulation --- p.26 / Chapter 1.2.3.2.6 --- Alcoholysis and Aminolysis --- p.27 / Chapter 1.2.3.2.7 --- Hydroarylation --- p.28 / Chapter 1.2.3.2.8 --- Arylative Ring Expansion with Alkynes --- p.29 / Chapter 1.3 --- Water as An Oxidizing Agent --- p.29 / Chapter 1.3.1 --- Water-Gas Shift Reaction --- p.30 / Chapter 1.3.2 --- Hydration of C-C π-Bond --- p.31 / Chapter 1.3.3 --- Cleavage of C≡C Bond --- p.31 / Chapter 1.3.4 --- Oxidation of C-H Bond --- p.32 / Chapter 1.4 --- Transition Metal Hydroxide Chemistry --- p.33 / Chapter 1.4.1 --- Preparation of Group 9 Metal Hydroxides --- p.34 / Chapter 1.4.1.2 --- Ligand Substitution --- p.34 / Chapter 1.4.1.3 --- Oxidative Addition --- p.34 / Chapter 1.4.1.4 --- Hydrolysis --- p.35 / Chapter 1.4.2 --- Chemistry of Transition Metal Hydroxide --- p.35 / Chapter 1.5 --- Introduction to Porphyrins and Group 9 Metalloporphyrins --- p.37 / Chapter 1.5.1 --- Porphyrin Ligand --- p.37 / Chapter 1.5.2 --- Metalloporphyrins --- p.38 / Chapter 1.5.3 --- Chemistry of Group 9 Metalloporphyrins --- p.39 / Chapter 1.5.3.1 --- M[superscript I](por) Chemistry --- p.40 / Chapter 1.5.3.2 --- M[superscript II](por) Chemistry --- p.41 / Chapter 1.5.3.3 --- M[superscript III](por) Chemistry --- p.44 / Chapter 1.5.4 --- Equilibration of MI(por), MI (por) and MIII(por) --- p.46 / Chapter 1.5.5 --- Chemistry of Group 9 Metalloporphyrin Hydroxide --- p.47 / Chapter 1.5.5.1 --- Metalloether Formation --- p.47 / Chapter 1.5.5.2 --- Reductive Dimerization --- p.48 / Chapter 1.5.5.3 --- Oxidation --- p.49 / Chapter 1.5.5.4 --- Carbon-Hydrogen Bond Activation --- p.50 / Chapter 1.5.5.5 --- Carbon-Carbon Bond Activation --- p.51 / Chapter 1.6 --- Scope of Thesis --- p.52 / Chapter Chapter 2 --- Carbon(CO)-Carbon(α) Bond Activation of Ketones with Rhodium(lII) Porphyrin Complexes --- p.63 / Chapter 2.1 --- Introduction --- p.63 / Chapter 2.2 --- Objectives of the Work --- p.66 / Chapter 2.3 --- Preparation of Starting Materials --- p.66 / Chapter 2.3.1 --- Synthesis of Porphyrin --- p.66 / Chapter 2.3.2 --- Synthesis of Rhodium(III) Porphyrin Chloride --- p.67 / Chapter 2.3.3 --- Synthesis of Rhodium(III) Porphyrin Methyl --- p.67 / Chapter 2.3.4 --- Synthesis of Rh[superscript III](ttp)H --- p.68 / Chapter 2.3.5 --- Synthesis of Rh[superscript II]₂(ttp)₂ --- p.68 / Chapter 2.3.6 --- Synthesis of Rh[superscript I](ttp)-Na⁺ --- p.68 / Chapter 2.4 --- Optimization of Reaction Conditions with Acetophenone --- p.68 / Chapter 2.4.1 --- Reaction with Rh[superscript III](ttp )OTf, Rh[superscript III](ttp)Cl and Rh[superscript III](ttp)Me --- p.68 / Chapter 2.4.2 --- Temperature Effect --- p.70 / Chapter 2.4.3 --- Porphyrin Ligand Effect --- p.70 / Chapter 2.5 --- Substrate Scope of the CCAReaction --- p.71 / Chapter 2.5.1 --- CCA of Acetophenones --- p.71 / Chapter 2.5.2 --- CCA of Aromatic and Aliphatic Ketones --- p.72 / Chapter 2.6 --- Low Temperature CCA with Isopropyl Ketones --- p.76 / Chapter 2.7 --- Oxidation of the C(CO)-C(α) Bond --- p.77 / Chapter 2.8 --- Water as a Source of Oxidant --- p.80 / Chapter 2.9 --- Regioselectivity of CCA --- p.81 / Chapter 2.1 --- 0 X-ray Structure Determination --- p.83 / Chapter 2.11 --- Mechanistic Studies --- p.92 / Chapter 2.11.1 --- Proposed Mechanism --- p.92 / Chapter 2.11.2 --- Aldol Condensation Catalyzed by Rh(ttp)X (X = Me or Cl) --- p.93 / Chapter 2.11.3 --- Carbon-Hydrogen Bond Activation with Rh(ttp)X (X = Me or Cl) --- p.94 / Chapter 2.11.4 --- Hydrolysis of the α-CHA Product 100 --- p.100 / Chapter 2.11.5 --- Carbon(CO)-Carbon(α) Bond Oxidation with Rh(ttp)OH --- p.102 / Chapter 2.11.6 --- Dehydrogenation of Alcohol --- p.108 / Chapter 2.11.7 --- Thermodynamic Consideration --- p.109 / Chapter 2.12 --- Conclusion --- p.110 / Chapter Chapter 3 --- Carbon(CO)-Carbon(α) Bond Activation of Ketones with Cobalt(II)Porphyrin Complexes --- p.114 / Chapter 3.1 --- Introduction --- p.114 / Chapter 3.2 --- Objectives of the Work --- p.115 / Chapter 3.3 --- Preparation of Starting Materials --- p.115 / Chapter 3.3.1 --- Synthesis of H₂(tp-clPP) --- p.115 / Chapter 3.3.2 --- Synthesis of Co[superscript II] (por) --- p.116 / Chapter 3.4 --- Strategies of C(CO)-C(α) Bond Activation with Cobalt(II) Porphyrins --- p.116 / Chapter 3.5 --- Optimization of Reaction Conditions with Diisopropyl Ketone --- p.118 / Chapter 3.5.1 --- Solvent Effect --- p.118 / Chapter 3.5.2 --- Water Effect --- p.119 / Chapter 3.5.3 --- PPh3 Effect --- p.120 / Chapter 3.5.4 --- Porphyrin Ligand Effect --- p.121 / Chapter 3.5.5 --- Temperature Effect --- p.122 / Chapter 3.6 --- CCA of Isopropyl Ketones --- p.123 / Chapter 3.7 --- X-ray Structure Determination --- p.126 / Chapter 3.8 --- Mechanistic Studies --- p.131 / Chapter 3.8.1 --- Proposed Mechanism --- p.131 / Chapter 3.8.2 --- Disproportionation of Co[superscript II](ttp) with Water --- p.132 / Chapter 3.8.3 --- Dehydrogenation of Co[superscript III](ttp)H --- p.132 / Chapter 3.8.4 --- C(CO)-C(α) Bond Activation --- p.134 / Chapter 3.8.5 --- Dehydrogenation of the Alcohol --- p.134 / Chapter 3.8.6 --- Overall Enthalpy Change --- p.134 / Chapter 3.9 --- Stoichiometric Functionalization --- p.135 / Chapter 3.10 --- Conclusion --- p.138 / Chapter Chapter 4 --- Comparison on Carbon-Carbon Bond Activation by Cobalt, Rhodium and Iridium Porphyrin --- p.142 / Chapter 4.1 --- Introduction --- p.142 / Chapter 4.2 --- Reactivities of Metalloporphyrins --- p.143 / Chapter 4.3 --- Thermodynamic of CCA --- p.144 / Chapter 4.4 --- Rate of CCA --- p.147 / Chapter 4.5 --- Scope and Reactivities of Ketones --- p.147 / Chapter 4.6 --- Regioselectivities --- p.149 / Chapter 4.7 --- Chemoselectivity --- p.150 / Chapter 4.8 --- Conclusion --- p.152 / Chapter Chapter 5 --- Experimental Section --- p.153 / Appendices --- p.181
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_328022 |
| Date | January 2012 |
| Contributors | Fung, Hong Sang., Chinese University of Hong Kong Graduate School. Division of Chemistry. |
| Source Sets | The Chinese University of Hong Kong |
| Language | English, Chinese |
| Detected Language | English |
| Type | Text, bibliography |
| Format | electronic resource, electronic resource, remote, 1 online resource (x, 248 leaves) : ill. (some col.) |
| Rights | Use of this resource is governed by the terms and conditions of the Creative Commons “Attribution-NonCommercial-NoDerivatives 4.0 International” License (http://creativecommons.org/licenses/by-nc-nd/4.0/) |
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