chapter 2 palladium catalysts in suzuki cross- coupling reaction

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ABSTRACT SHORT-TIME SUZUKI REACTIONS OF ARYL HALIDES CATALYZED BY PALLADIUM-LOADED NaY ZEOLITE UNDER AEROBIC CONDITIONS The palladium-catalyzed Suzuki cross-coupling reaction is a powerful methods used in the synthesis of biaryl compounds. In this study, the Suzuki reactions of aryl bromides and chlorides with arylboronic acid were carried out over a Pd(NH3)4 2+ -loaded NaY type zeolite. On the basis of our results, the Pd(NH3)4 2+ -loaded NaY zeolite was found to be highly active for the Suzuki reactions of wide range of aryl bromides and electron poor aryl chlorides at low Pd concentrations (0.1-0.001mol %Pd), in air and at short times (5-45 minutes). The presence of relatively large amount of zeolite (1-4 g) was crucial for the success of the reactions with aryl chlorides. It was determined that there was a synergistic effect of the water- zeolite pair on the reaction rate. It was found that reactions were catalyzed dissolved palladium species. However, the palladium was largely recovered and only traces of palladium remained within the solution at the end of reaction (
ÖZET ARİL HALOJENÜRLERİN HAVA ALTINDA PALADYUM YÜKLÜ NaY ZEOLİT KATALİZLİ KISA SÜRELİ SUZUKİ TEPKİMELERİ Paladyum katalizli Suzuki kenetlenme tepkimeleri biaril bileşiklerinin sentezinde kullanılan etkili bir metotdur. Bu çalışmada arilboronik asitlerle aril bromür ve klorürlerin Suzuki tepkimeleri Pd(NH3)4 2+ -yüklü NaY tipi zeolit ile gerçekleştirilmiştir. Sonuçlarımız doğrultusunda, Pd(NH3)4 2+ -yüklü NaY tipi zeolitin, hava altında ve düşük paladyum konsantrasyonunda (0.1-0.001 mol %Pd), kısa süre içerisinde (5-45 dakika). çeşitli aril bromür ve elektronca fakir klorürlerin Suzuki tepkimelerinde oldukça aktif olduğu gözlenmiştir. Göreceli olarak büyük miktarlarda zeolit varlığı (1-4 g) aril klorürlerin reaksiyonlarının başarısında kritik bir role sahipti. Tepkime verimliliğine zeolit-su bileşiminin sinerjistik etkisi olduğu saptanmıştır. Reaksiyonların çözünmüş paladyum ile katalizlendiği bulunmuştur. Bununla birlikte paladyum büyük ölçüde kazanılmış ve reaksiyon sonunda, çözelti içerisinde iz miktarda paladyuma rastlanmıştır (
Page 1 and 2: SHORT-TIME SUZUKI REACTIONS OF ARYL
Page 3: ACKNOWLEDGEMENTS Firstly, I’d lik
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 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
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
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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
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REFERENCES Albisson, D.A., Bedford,
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Choudary, B.M., Madhi, S., Chowdari
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Heiden, M. Plenio, H. 2004. ‘‘H
Page 89 and 90:
Coupling Reactions of Aryl Chloride
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Phan, N.T.S., Brown, D.H., Styring,
Page 93 and 94:
Wolfe, J.P., Singer, R.A., Yang, B.
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Figure A.1. 13 C NMR of 1-phenylnap
Page 97 and 98:
Figure A.3. 13 C NMR of 2-acetylbip
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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
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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
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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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chapter 2 palladium catalysts in suzuki cross- coupling reaction

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