Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1986 Palladium-Catalyzed Vinylic Substitution of Aryl Halides on Polymeric Nitrogen Supports. Chia-hsing Sun Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Sun, Chia-hsing, "Palladium-Catalyzed Vinylic Substitution of Aryl Halides on Polymeric Nitrogen Supports." (1986). LSU Historical Dissertations and Theses. 4268. https://digitalcommons.lsu.edu/gradschool_disstheses/4268 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. 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Dissertation contains pages with print at a slant, filmed as received_________ 16. Other___________________________________________________________________ University Microfilms International Palladium-Catalyzed Vinylic Substitution of Aryl Halides on Polymeric Nitrogen Supports A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Chia-Hsing Sun B.S., Tunghai University, 1976 M.S., Tsinhua University, 1980 May 1986 ACKNOWLEDGEMENT The firm instruction and guidance by Dr. William H. Daly, the director of this research is sincerely appreciated. However, the work could not have been completed without the constant spiritual support and instruction of the author's parents, to whom this work is dedicated. The author further appreciates sharing discussions and experiences with Mr. Amnard Sittatrukul. Financial support by Louisiana State University was provided for the author throughout the course of his research. The author gratefully acknowledges financial assistance from the Dr. Charles E. Coates Memorial Fund of the Louisiana State University Foundation for expenses incurred in the publication of this Dissertation. i Table of Contents Page ACKNOWLEDGEMENT................................... i LIST OF T A B L E S .................................... vii LIST OF ILLUSTRATIONS..........................'. ix LIST OF FIGURES..................................... xi ABSTRACT.......................................... xil I. INTRODUCTION............................. 1 II. PALLADIUM-CATALYZED REACTIONS ........... 5 2.1 Introduction and Background. .... 5 2.2 Chemistry of Palladium Compounds (Inorganic and Organometallic Aspects) ........................... 7 2.2.1 Complexes of Palladium(o). 7 2.2.2 Properties of complexes of (PR3)ilP d ................. 10 2.2.3 Reactions of Palladium(o) complexes................. 11 2.2.4 [Pd(dba)g]...............13 2.2.5 Complexes of Pd ( I ) ........14 2.2.6 Complexes of Pd(II)....... 15 2.3 Application of Organopalladium Catalysiss in Homogeneous Catalysis in Organic Synthesis................. 18 2.3.1 Arylation of Alkenes .... 22 ii 2.3.2 Vinylation of Alkenes. 40 2.3.3 Palladium-catalyzed Nucelo- philic Additions to Alkenes. 49 III. POLYMER SUPPORTED CATALYSIS........... 62 3.1 Introduction..................... 62 3.2 Synthesis of Polymer-Supported Catalysts ..... .............. 68 3.2.1 Functionalization of Preformed Polymers ........ 71 3.2.2 Polymerization of Monomeric Ligands....................... 81 3.2.3 Polymerization of Monomeric Organometallic Complexes . 86 3.2.4 Macromolecular Immobili­ zation ............ 89 3.2.5 "Single Crystal" Polymer Support....................... 91 3.3 Reaction Aspects of Polymer- Supported Catalysts.................91 IV. RESULT AND DISCUSSION.................... 104 4.1 Synthesis of Dipyridyl Derivatives for Immobilization on Polymer . 104 4.2 Synthesis of Pyridine Derivatives for Immobilization on a Polymer Support............................ 111 iii 4.3 Homogeneous Palladium-Catalyzed Vinylic Substitution............ 115 4.4 Substituent and Concentration Effect of Pyridine and Dipyridyl. 122 4.5 Substituent Effect of Aryl Halides........................ 130 4.6 Polymer-Supported Catalyst. 140 4.7 Conclusion...................... 152 V. EXPERIMENTAL SECTION ................. 154 General Information.................. 154 Specific Reaction Procedures ........ 155 1 . 2-(2-pyridyl)cinchoninic acid . 155 2. Ethyl 2-(2-pyridyl)cinchoninate Method A ........................ 156 Method B ........................ 156 3. N-(3-propylamino)-2-(2-pyridyl)- cinchoninamide.................. 157 4. Benzyl 2-(2-pyridyl)cinchoninate. 158 5. 4-pyridine carboxylic acid. 159 6. Benzyl 4-pyridinecarboxylate. 159 7. 4-Benzyloxypyridine Method A (attempted)............ 160 Method B ........................ 161 Method C ........................ 161 8. 4-Hydroxypyridlne-1-oxide .... 162 9. 3-Benzyloxypyridine ............ 163 iv 10. 4-Benzyloxypyridine-1-oxide . 163 11. Vinylbenzyl acetate ............. 164 12. 4-Vinylbenzyloxypyridine-1-oxide (attempted).................... 164 13. 4-Vinylbenzyloxypyridine......... 165 14. Vinylbenzyl 2-(2-pyridyl)- cinchoninate.................... 166 15. Vinylbenzyl 4-pyridinecarboxylate 16. PdC0Ac)2......................... 168 17. Terephthaldehyde................. 168 18. p-Bromo benzylalcohol ........... 169 19. 4-Vinylbenzaldehyde (attempted) . 170 20. Dibenzalacetone (DBA) ........... 171 21. Pd2(DBA)3CHCl3 ................... 171 22. 15? DVB cross-linked [poly- vinylpyridine)] ................ 172 23. DVB cross-linked [poly- (vinylbenzyloxy-4-pyridine)]. 173 24. DVB cross-linked [poly- (vinylbenzyl-4-pyridine carboxylate) ] .................. 173 25. DVB cross-linked [poly- (vinylbenzyl 2-(2-pyridyl) cinchoninate) ].................. 174 26. 15? DVB cross-linked [poly- (vinylpyridine) PdCl2).......... 174 v 27. [PolyCvinylbenzyloxy-4-pyridine) PdClg 3........................... 175 28. DVB cross-linked Epoly- Cvinylbenzyl 4-pyridine- carboxylate) PdCl23 ............ 175 29. General vinylic substitution procedure for homogeneous catalysis....................... 175 30. General vinylic substitution procedure for heterogeneous * catalysis...................... 176 BIBLIOGRAPHY ................................... 179 APPENDIX Attempted synthesis of p-vinylbenzyl chloride................................... 201 VITA ......... ................................. 209 vi LIST OF TABLES NUMBER Page I. Regiochemistry of Phenylation............. 26 II. The relative rates of phosphonium salt formation.................... 32 III. Influence of substituted