Recommended
More Related Content
What's hot
What's hot (18)
Similar to Applications of New Phosphine ligands in Metal-Catalyzed Reaction
Similar to Applications of New Phosphine ligands in Metal-Catalyzed Reaction (20)
Recently uploaded
Recently uploaded (20)
Applications of New Phosphine ligands in Metal-Catalyzed Reaction
- 4. 4 ‹#› 4Gowrisankar, Germany Ø 80 % of biologically active compounds are aromatic/heteroaromatic systems Ø Angew. Chem. 2000, 112, 4315-4317. Ø Chem. Commun. 2000, 2475-2476. Ø Chem. Comm. 2004, 38-39. Ø Chem. E. J. 2001, 7, 2908-2915. Ø Synlett 2000, 1589-1592. Functionalization of Aromatic Compounds × Angew. Chem. Int. Ed. 2003, 41, 4056-4057. × Adv. Synth. Catal. 2002, 344, 209. × Tetrahedron Lett. 2001, 6707-6710. × Angew. Chem. Int. Ed. 2003, 42, 1559- 1661. × J. Mol. Cat. 2002, 182-183, 515. × Chem. Eur. J. 2004, 10, 2983-2990. Ø Angew. Chem. 2001, 113, 2940-2943. Ø Chem. Eur. J. 2004, 10, 746-757. ØAngew. Chem. Int Ed. 2006, 45, 154-156.
- 5. 5 ‹#› 5Gowrisankar, Germany Aryl-X Activation: A Powerful Tool Advantages ü High Selectivity üMore Reactive ü Lower Catalyst Loading ü High Substrates Scope ü Scale-up is not problematic ü Reduction of Waste L. Ackermann H. Alper C. Amatore R. Bedford I. P. Beletskaya M. Beller S. L. Buchwald H. Doucet G. Fu F. Glorius J. F. Hartwig W. A. Herrmann A. Jutand K. Köhler M. Kwong G. Li C. Najera S. P. Nolan J. G. de VriesA. Hallberg Important contributions in catalyst developments:
- 6. 6 ‹#› 6Gowrisankar, Germany Heteroaryl-type Triarylphosphines oxide Trialkylphosphines Phosphine ligands for Pd catalyzed reactions Phosphine Ligands ü Solubility of the Active Species ü Reactivity of the Catalyst ü Usually Strong σ Donors and Weak π Acceptors ü Oxidative Addition Step needed
- 8. 8 ‹#› 8Gowrisankar, Germany Importance of C-O Bond Ø Buckingham, J. Dictionary of Natural Products; University Press: Cambridge, MA, 1994. Czarnik, A. W. Acc. Chem. Res. 1996, 29, 112. üThere are few methods on palladium catalyzed C-O bond formation
- 9. 9 ‹#› 9Gowrisankar, Germany C-O Bond Formation: Ligand Screening β-H elimination Reductive elimination Ø S. Gowrisankar, A. G. Sergeev, P. Anbarasan, A. Spannenberg, H. Neumann, M. Beller, J. Am. Chem. Soc. 2010, 132, 11592 –11598. Oxidative esterfication product dehalogenated üElectron rich phosphine enhances rate of oxidative addition üBulkness of Adamantyl accelerates reductive elimination Oxidative addition üSubstituents in 3,5-position prevent oxidation at Phosphine üConvenient for synthesis
- 10. 10 ‹#› 10Gowrisankar, Germany C-O Bond Formation: Substrates Scope üHigher chain alcohols üFG attached alcohols üSterically Hindered Substrates üElectron Donating Group üElectron Withdrawing Group üHeteroaromatic Substrates Ø S. Gowrisankar, A. G. Sergeev, P. Anbarasan, A. Spannenberg, H. Neumann, M. Beller, J. Am. Chem. Soc. 2010, 132, 11592 –11598.
- 11. 11 ‹#› 11Gowrisankar, Germany C-O Bond Formation: Synthesis of Butoxycaine ØThe Merck index: An encyclopedia of chemicals, drugs, and biologicals (12th edition), page no. 254 compound 1566 üSelectivity of primary alcohols Synthesis of Butoxycaine üLocal Anesthetic Synthetic Drug Ø S. Gowrisankar, A. G. Sergeev, P. Anbarasan, A. Spannenberg, H. Neumann, M. Beller, J. Am. Chem. Soc. 2010, 132, 11592 –11598. 1o vs 2o Alcohols & 1o vs 3o Alcohols
- 12. 12 ‹#› 12Gowrisankar, Germany Synthesis of Ligand C-O Bond Formation: Synthesis of Ligand Ø S. Gowrisankar, A. G. Sergeev, P. Anbarasan, A. Spannenberg, H. Neumann, M. Beller, J. Am. Chem. Soc. 2010, 132, 11592 –11598. ü Substituents in 3,5-position prevent oxidation at Phosphine üBulkly Adamantyl accelerates reductive elimination üElectron rich phosphines enhance rate of oxidative addition üConvenient for synthesis
- 13. 13 ‹#› 13Gowrisankar, Germany C-O Bond Formation: Synthesis of Anisoles Ø Gowrisankar, S.; Neumann, H.; M. Beller, Chem. Eur. J. 2012, (in press). ü First reported deutrated Anisoles ü EDG, EWG and Heteroaryl system
- 14. 14 ‹#› 14Gowrisankar, Germany C-O Bond Formation: Synthesis of Arylpropargyl Ethers Conditions: Pd(OAc)2 (1 mol%), o-bromotoluene (1.0 equiv.) pent-2-yn-1-ol (1.3 equiv.), Ligand (2 mol%), Cs2CO3 (1.5 equiv.) Toluene, 80 °C, GC yield Ø Gowrisankar, S.; Neumann, H.; M. Beller, ChemCatChem 2011, 3, 1439-1441. ü Oxidative Ester product ü Oxidation product ü Reduced Alkyne
- 18. 18 ‹#› 18Gowrisankar, Germany ØS. Gowrisankar, H. Neumann, M. Beller, Angew. Chem. Int. Ed. 2011, 50, 5139-5143. the green tissue of plants Oxidative Esterification: Substrates Scope ü Long chain alcohols ü Aliphatic-aliphatic coupling ü Heteroaromatic alcohols
- 19. 19 ‹#› 19Gowrisankar, Germany ü During Oxidative esterification Ligand BuPAd2 converted to O=PBuAd2 oxide Oxidation of Alcohols Ø S. Gowrisankar, H. Neumann, M. Beller, Angew. Chem. Int. Ed. 2011, 50, 5139-5143.
- 20. 20 ‹#› 20Gowrisankar, Germany Conditions: 1-Napthylmethanol (0.63 mmol), 3 mol% Pd(OAc)2 (0.018 mmol), 5 mol% L (0.032 mmol), 30% pyridine or 50% NaOAc, 100 mg MS4 Å, 1 mL toluene, 80-85 °C, 1 bar O2, 10-20 h. GC yield. Ø Gowrisankar, S.; Gördes, D.; Jiao, H.; Neumann, H.; Beller, M. will be submitted. Oxidation of Alcohols: Ligand Screening
- 21. 21 ‹#› 21Gowrisankar, Germany Oxidation: Substrates Scope Ø Gowrisankar, S.; Gördes, D.; Jiao, H.; Neumann, H.; Beller, M. will be submitted. ü FG tolerance ü 1o and 2o Allylic Alcohols ü 1o and 2o Aliphatic alcohols Conditions: Alcohols, 3 mol% Pd(OAc)2, 5 mol% L 30% pyridine or 50% NaOAc, 100 mg MS4 Å, 1 mL toluene, 80-85 °C, 1 bar O2, 10-20 h.
- 22. 22 ‹#› 22Gowrisankar, Germany 31 P NMR at 54 ppm NMR Experiments Unexpected results Ø Gowrisankar, S.; Gördes, D.; Jiao, H.; Neumann, H.; Beller, M. will be submitted. 31 P NMR of O=PBu3 at 49 ppm
- 23. 23 ‹#› 23Gowrisankar, Germany 1. 2. 3. 4. 5. 6. HRMS Analysis Dr. Dirk Gördes, Center for Life Science Automation (celisca), Germany
- 24. 24 ‹#› 24Gowrisankar, Germany Phosphomide Ligands Future Work: Design of New Class of Phosphomide Ligands ü Phosphomide used as ligand ü Mostly neglected ligand in phosphine chemistry ü Electron withdrawing effect (adjacent to a carbonyl group) ü Oxygen lone pair to delocalise towards the carbon atom Acid chloride Dialkyl(aryl)phosphine ØGoerlich, J. R.; Muller, C.; Schmutzler R. Phosphorus, Sulfur Silicon Relat. Elem. 1993, 85, 193–205. ØBarron, A. R.; Hall, S.W.; Cowley, A. H. J. Chem. Soc. Chem. Commun. 1987, 1753–1754. ØKunzek, H.; Braun, K.; Nesener, E.; Ruhlmann, K. J. Organomet. Chem. 1973, 49, 149.
- 25. 25 ‹#› 25Gowrisankar, Germany Synthesis of ligands ü R = Ph, Cy, tBu, Ad ü Heteroaryl type phosphomide
- 26. 26 ‹#› 26Gowrisankar, Germany Hydrogenation of Carbondioxide Ø Green House Effect Ø Global Warming ØCO2 deposit and disposal
- 27. 27 ‹#› 27Gowrisankar, Germany Catalytic Hydrogenation of CO2, sodium bicarbonate: References Ø Jessop, et. al J. Am. Chem. Soc. 2002, 124, 7963 Ø F. Joó, et. al. Applied Catalysis A: General 2003, 255, 59–67 Ø Y. Himeda et. al Organometallics 2007, 26, 702 ØR. Noyori, et. al Nature 1994, 368, 231–233. ØBeller, et. al. ChemSusChem 2010, 3, 1048 ØLaurenczy, et. al Inorg. Chem. Commun. 2007, 10, 558 ØLaurenczy, et. al Chem. Eur. J. 2007, 13, 3886–3899.
- 28. 28 ‹#› 28Gowrisankar, Germany Ø I am interested to prepare new class of Phosphomide based phosphine ligands used in metal-catalyzed hydrogenation for CO2 and NaHCO3. Summary Ø Efficient development C-O cross coupling reactions by using Modified pyrazole based phosphine ligand Ø Pd-catalyzed Oxidative esterfication Cross esterification and Self esterification (by product is water) Ø Phosphine oxide is also efficiently for the Oxidation of primary alcohols and secondary alcohols
- 29. 29 ‹#› 29Gowrisankar, Germany Prof. Matthias BellerProf. Jae Nyoung Kim Acknowledgment Ø Dr. Helfried Neumann (Group Leader) Ø Dr. Bäumann (Analytical Department) Ø All my colleagues in LIKAT Ø Leibniz institute (Funding)
- 30. 30 ‹#› 30Gowrisankar, Germany Leibniz-Institut für Katalyse (LIKAT) Rostock Thank you for your kind attentionThank you for your kind attention!!!