chapter 2 palladium catalysts in suzuki cross- coupling reaction

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R Table 3.1. Examples from literature on Suzuki reactions of aryl halides X + B(OH) 2 R' Entry R Catalyst/ Ligand Pd / ligand R Reaction Conditions R' Yield% Ref. 1 H, 2-CH3, 4-CH3 21 aq.KOH, 25 °C 67-91 Uozumi et al. 1999 2 4-: CHO, COCH3, 22 K3PO4, DMF, 100 Phan et al. CN 90 °C, 24h, 2004 3 4-: COCH3, CH3, Pd(OAc)2/ KF, THF, RT, 42-75 Inada and OMe 24 48-60 h Miyaura 2000 4 Ph Pd(0) on 100 °C, 4h 29-99 Kabalka KF/Al2O3 et al. 1999 5 4-: NO2, CF3, CN, Pd/C DMA/H2O, 79-95 Leblond K2CO3, 80°C et al. 2001 6 4-: NO2, OCH3 31 Cs2CO3, dioxane, 100 °C, Ar atm, 2h 7 4-: COCH3, COOH, CH3 , H, 2-: CN, NO2 8 H, CN, Cl, OCH3, CH2Br 9 4-: H, -OCH3, -CN, 32 K2CO3, water, 2h, 100 °C 33 xylene, K2CO3, 95 °C 35 o-xylene, N2 atm, 95 °C 49- 97 Blanco et al. 2006 73-99 Baleizao et al. 2003 88-98 Mobufu et al. 2001 75-100 Paul and Clark 2003 Gurbuz et al. prepared and characterized silica supported 3-(4,5dihydroimidazol-1-yl)-propyltriethoxysilanedichloropalladium(II), 34 (Figure 3.11), and 34
utilized them in Heck and Suzuki coupling reactions of iodo-, bromo- and chloroarenes (Figure 3.11). The heterogeneous catalyst was reusable many times (Gurbuz et al. 2003). In 2003, Paul and Clark used a novel silica-supported palladium catalyst, 35 (Figure 3.11), for Suzuki reactions of aryl and polyaryl bromides with phenylboronic acid (Table 3.1, entry 9). The key features of the catalyst included rapid reactions, excellent catalyst recyclability and total stability under reaction conditions. The catalyst which has a very low loading of palladium was defined as completely heterogeneous and highly stable under reaction conditions (Paul and Clark 2003). Si O Si N N Cl Pd Cl N N O Cl Si O Si O Si 34 Si N N Pd Cl N N AcO OAc Pd O O N Silica 35 Si N O CH 3 Figure 3.11. The immobilized Pd(II) species on silica supports Clays are also special inorganic solids since they have well-defined structures and pores with molecular dimensions, which can solvate the adsorbed molecules and provide solvent-like environments (Smith and Nontheisz 1999). Varma et al. reported PdCl2/tetraphenylphosphonium bromide-intercalated clay as a heterogeneous catalyst for Suzuki coupling of aryl bromides and iodides (Varma et al. 1999, Varma and Naicker 1999a, Varma and Naicker 1999b). The deposition of palladium salts on hydrotalcite which is a naturally occurring mineral of the layered double hydroxide family that constitutes a major class of anionic 35
Page 1 and 2: SHORT-TIME SUZUKI REACTIONS OF ARYL
Page 3 and 4: ACKNOWLEDGEMENTS Firstly, I’d lik
Page 5 and 6: ÖZET ARİL HALOJENÜRLERİN HAVA A
Page 7 and 8: 3.2.2. Catalysts Anchored to Inorga
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: SO 2NH N Pd SO 2 N SO 2 NH NH H O1.
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
Page 67 and 68: Table 5.2. The effect of base on Pd
Page 69 and 70: Table 5.4. The Optimization of Pd-N
Page 71 and 72: H 3COC Table 5.5. Effect of zeolite
Page 73 and 74: Table 5.6. Pd(NH3)4 2+ -loaded NaY
Page 75 and 76: The type of other organic co-solven
Page 77 and 78: yield was very low (Table 5.8, entr
Page 79 and 80: evealed excellent reactivity toward
Page 81 and 82: 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,
Page 93 and 94: Wolfe, J.P., Singer, R.A., Yang, B.
Page 95 and 96: Figure A.1. 13 C NMR of 1-phenylnap
Page 97 and 98:
Figure A.3. 13 C NMR of 2-acetylbip
Page 99 and 100:
Figure A.5 . 13 C NMR of 2-methoxyb
Page 101 and 102:
Figure A.7. 13 C NMR of 2-methylbip
Page 103 and 104:
Figure A.9. 13 C NMR of 2-phenylnap
Page 105 and 106:
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
Page 113 and 114:
Figure A.19. 13 C NMR of 4-methoxyb
Page 115 and 116:
Figure A.21. 13 C NMR of 4-methylbi
Page 117 and 118:
Figure A.23. 13 C NMR of 4-phenylbe
Page 119 and 120:
Figure A.25. 13 C NMR of 4-acetylbi
Page 121 and 122:
Figure A.27. 13 C NMR of 4-cyanobip
Page 123 and 124:
Figure A.29. 13 C NMR of 4-nitrobip
Page 125 and 126:
Figure A.31. 13 C NMR of 4-phenylan
Page 127 and 128:
APPENDIX B MASS SPECTRUMS OF SUZUKI
Page 129 and 130:
Figure B.2. Mass spectrum of 2-acet
Page 131 and 132:
Figure B.4. Mass spectrum of 2-meth
Page 133 and 134:
Figure B.6. Mass spectrum of 3-acet
Page 135 and 136:
Figure B.8. Mass spectrum of 3-phen
Page 137 and 138:
Figure B.10. Mass spectrum of 4-phe
Page 139 and 140:
Figure B.12. Mass spectrum of 4-met
Page 141 and 142:
Figure B.14. Mass spectrum of 4-cya
Page 143:
Figure B.16. Mass spectrum of 4-met
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chapter 2 palladium catalysts in suzuki cross- coupling reaction

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