chapter 2 palladium catalysts in suzuki cross- coupling reaction

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TABLE OF CONTENTS LIST OF FIGURES ........................................................................................................... ix LIST OF TABLES.............................................................................................................xii CHAPTER 1. INTRODUCTION ....................................................................................... H1 CHAPTER 2. PALLADIUM CATALYSTS IN SUZUKI CROSS-COUPLING REACTION ................................................................................................ H3 2.1. Palladium Metals as Catalysts in Organic Syntheses ............................. H4 2.1.1. Palladium as a Transition Metal ....................................................... H4 2.1.2. The Coordination Geometry of Organopalladium Compounds ....... H5 2.1.3. The Characteristic Features of Pd and Pd-C Bonds.......................... H5 2.1.4. Palladium-Catalyzed Cross-Coupling Reactions.............................. H6 2.2. The Suzuki Reactions ............................................................................. H8 2.2.1. Mechanism of Suzuki Coupling Reactions....................................... H9 2.2.1.1. Oxidative Addition .................................................................. H9 2.2.1.2. Transmetallation .................................................................... H10 2.2.1.3. Reductive Elimination ........................................................... H11 2.2.2. Reaction Conditions Affecting the Suzuki Reactions..................... H12 2.2.2.1. Substrate Effect...................................................................... H12 2.2.2.2. Halogen Effect ....................................................................... H13 2.2.2.3. Ligand Effect ......................................................................... H13 2.2.2.4. Base Effect............................................................................. H18 2.2.2.5. Additive Effect....................................................................... H19 2.2.2.6. Solvent and Temperature Effects........................................... H20 2.2.2.7. Pressure and Microwave Heating Effects.............................. H20 CHAPTER 3. THE HETEROGENEOUS SUZUKI CROSS-COUPLING REACTIONS............................................................................................ H22 3.1. The Immobilization to Liquid Phase .................................................... H23 3.2. The Immobilization to Insoluble Support............................................. H26 3.2.1. Attachment to Polymer Supports.................................................... H27 vi
3.2.2. Catalysts Anchored to Inorganic Solids.......................................... H31 3.3. Zeolite supported palladium catalysts in the Suzuki Reactions............ H37 3.3.1. Structural Features of Zeolite ......................................................... H37 3.3.2. The Advantages of Zeolites ............................................................ H38 3.3.3. Preparation of Zeolite-Supported Metal Catalysts.......................... H41 CHAPTER 4. EXPERIMENTAL STUDY ...................................................................... H43 4.1. Palladium-Loaded Zeolite Catalyst Preparation ................................... H43 4.1.1. Palladium-Loaded Zeolite Catalyst Characterization ..................... H44 4.2. General Procedures for the Suzuki Coupling Reactions....................... H44 4.3. Characterization of Products................................................................. H45 4.3.1. GC Method ..................................................................................... H45 4.3.1.1. Calculation of Reactant and Product Amount on GC............ H46 4.3.1.2. Calculation of Reactant Conversion, Product Yield and Recovery ................................................................................. H47 4.4. Purification of the Products .................................................................. H48 4.5. Leaching Test........................................................................................ 52 CHAPTER 5. RESULTS AND DISCUSSIONS ............................................................. 53 5.1. The Suzuki Reactions of Aryl Chlorides .............................................. 53 5.1.1. Pd-NaY Catalyzed Suzuki Reaction of 4-Chloroacetophenone with Phenylboronic Acid ................................................................. 53 5.1.2. Pd(NH3)4 2+ -loaded NaY type Zeolite Catalyzed Suzuki Cross- Coupling Reaction of Aryl Chlorides .............................................. 60 5.1.3. The Leaching Test for Suzuki Reaction of Aryl Chlorides ............ 61 5.2. The Suzuki Reactions of Aryl Bromides .............................................. 62 5.2.1. The Optimization of Pd(NH3)4 2+ -Loaded NaY Type Zeolite Catalyzed Suzuki Reactions of 4-Bromoanisole with Phenylboronic Acid ......................................................................... 62 5.2.2. Pd(NH3)4 2+ -Loaded NaY Type Zeolite Catalyzed Suzuki Reactions of Aryl Bromides and ArylBoronic Acids ...................... 65 5.2.3. The Leaching Test for the Suzuki Reactions of Aryl Bromides..... 68 CHAPTER 6. CONCLUSIONS ....................................................................................... 69 vii
Page 1 and 2: SHORT-TIME SUZUKI REACTIONS OF ARYL
Page 3 and 4: ACKNOWLEDGEMENTS Firstly, I’d lik
Page 5: ÖZET ARİL HALOJENÜRLERİN HAVA A
Page 9 and 10: LIST OF FIGURES Figure Page Figure
Page 11 and 12: Figure A.27. 13 C NMR of 4-cyanobip
Page 13 and 14: CHAPTER 1 INTRODUCTION The palladiu
Page 15 and 16: CHAPTER 2 PALLADIUM CATALYSTS IN SU
Page 17 and 18: 2.1.2. The Coordination Geometry of
Page 19 and 20: R 1 R 1 4. Sonogashira Reaction: H
Page 21 and 22: 2.2.1. Mechanism of Suzuki Coupling
Page 23 and 24: As a result, organic group or hydri
Page 25 and 26: 2.2.2.2. Halogen Effect Nearly all
Page 27 and 28: found to be excellent complexes for
Page 29 and 30: R Table 2.2. Examples from literatu
Page 31 and 32: L R Pd X R Pd L OR'' X L L + OR' R'
Page 33 and 34: omides and iodides is performed eff
Page 35 and 36: times for the transformation of a l
Page 37 and 38: R Br + (HO) 2B R' 5% Pd(OAc) 2 15%
Page 39 and 40: of insoluble solids are among the m
Page 41 and 42: could be reused multiple times. The
Page 43 and 44: 3.2.2. Catalysts Anchored to Inorga
Page 45 and 46: SO 2NH N Pd SO 2 N SO 2 NH NH H O1.
Page 47 and 48: utilized them in Heck and Suzuki co
Page 49 and 50: Smith et al introduced the use of P
Page 51 and 52: • Complexes immobilized in zeolit
Page 53 and 54: 3.3.3. Preparation of Zeolite-Suppo
Page 55 and 56: CHAPTER 4 EXPERIMENTAL STUDY 4.1. P
Page 57 and 58:
temperature, the catalyst was recov
Page 59 and 60:
amount of both reactant and product
Page 61 and 62:
4-Methoxybiphenyl: 1 H NMR (400 MHz
Page 63 and 64:
51 Table 4.1. Purification of coupl
Page 65 and 66:
CHAPTER 5 RESULTS AND DISCUSSIONS I
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Table 5.2. The effect of base on Pd
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Table 5.4. The Optimization of Pd-N
Page 71 and 72:
H 3COC Table 5.5. Effect of zeolite
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Table 5.6. Pd(NH3)4 2+ -loaded NaY
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The type of other organic co-solven
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yield was very low (Table 5.8, entr
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evealed excellent reactivity toward
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CHAPTER 6 CONCLUSIONS In this thesi
Page 83 and 84:
REFERENCES Albisson, D.A., Bedford,
Page 85 and 86:
Choudary, B.M., Madhi, S., Chowdari
Page 87 and 88:
Heiden, M. Plenio, H. 2004. ‘‘H
Page 89 and 90:
Coupling Reactions of Aryl Chloride
Page 91 and 92:
Phan, N.T.S., Brown, D.H., Styring,
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Wolfe, J.P., Singer, R.A., Yang, B.
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Figure A.1. 13 C NMR of 1-phenylnap
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Figure A.3. 13 C NMR of 2-acetylbip
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Figure A.5 . 13 C NMR of 2-methoxyb
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Figure A.7. 13 C NMR of 2-methylbip
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Figure A.9. 13 C NMR of 2-phenylnap
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Figure A.11. 13 C NMR of 3-acetylbi
Page 107 and 108:
Figure A.13. 13 C NMR of 3-methoxyb
Page 109 and 110:
Figure A.15. 13 C NMR of 3-phenylpy
Page 111 and 112:
Figure A.17. 13 C NMR of 4-acetyl-4
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Figure A.19. 13 C NMR of 4-methoxyb
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Figure A.21. 13 C NMR of 4-methylbi
Page 117 and 118:
Figure A.23. 13 C NMR of 4-phenylbe
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Figure A.25. 13 C NMR of 4-acetylbi
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Figure A.27. 13 C NMR of 4-cyanobip
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Figure A.29. 13 C NMR of 4-nitrobip
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Figure A.31. 13 C NMR of 4-phenylan
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APPENDIX B MASS SPECTRUMS OF SUZUKI
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Figure B.2. Mass spectrum of 2-acet
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Figure B.4. Mass spectrum of 2-meth
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Figure B.6. Mass spectrum of 3-acet
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Figure B.8. Mass spectrum of 3-phen
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Figure B.10. Mass spectrum of 4-phe
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Figure B.12. Mass spectrum of 4-met
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Figure B.14. Mass spectrum of 4-cya
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Figure B.16. Mass spectrum of 4-met
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