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Hetero Breslow -analogues the case of phosphorus

Műegyetem 1782. Hetero Breslow -analogues the case of phosphorus. Zsolt Kelemen , László N yulászi Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics nyulaszi@mail.bme.hu. Carbenes . NHC carbenes.

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Hetero Breslow -analogues the case of phosphorus

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  1. Műegyetem 1782 Hetero Breslow-analogues the case of phosphorus Zsolt Kelemen, László Nyulászi Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics nyulaszi@mail.bme.hu

  2. Carbenes NHC carbenes D. Martin, M. Soleilhavoup, G. Bertrand, Chem. Sci. 2011 2, 389-399 A. J. Arduengo et al. J. Am. Chem. Soc.1991,113, 361-363

  3. Carbene complexesNobel Prizes in Chemistry Richard R. Schrock 2005 Robert H. Grubbs 2005 Ernst Otto Fischer 1973 Yves Chauvin 2005

  4. Free NHC organocatalyzed reactions R. Breslow, J. Am. Chem. Soc. 1958, 80, 3719-3726 A. Berkessel, S.Elfert, V. R. Yatham, J. Neudörfl, N.E. Schlörer,J. H. Teles Angew. Chem. Int. Ed. 2012, 51, 12370 –12374

  5. Breslow-intermediate δ+ δ- Benzoin condensation

  6. B1-Vitamin, the Thiamin Transketolase

  7. Deoxi Breslow-intermediate δ- δ+ C. E. I. Knappke, J. M. Neudçrfl, A. J. Wangelin, Org. Biomol. Chem. 2010, 8, 1695N. Kuhn, M. Göhner, M. Steimann, Z. Naturforsch. B 2002, 57, 631 G. H. Alt, J. Org. Chem. 1968, 33, 2858.

  8. The phosporusanalogue δ- δ+ E. Fuchs, H. Heydt, M. Regitz, W. W. Schoeller, T. Busch, Tetrahedron Lett. 1989, 30, 5111-5114. E. Fuchs, B. Breit, H. Heydt, W. Schoeller, T. Busch, C. Krüger, P. Betz,M. Regitz, Chem. Ber. 1991, 124,2843-2855. A. N. Chernega, A. V. Ruban, V. D. Romanenko, L. N. Markovskii, A. A. Korkin, M. Y. Antipin, Y. T. Struchkov, Heteroatom Chem. 1991, 2, 229-241. L. Weber Eur. J. Inorg. Chem 2000 2425-2441 A.J. Arduengo III ,  C. J. Carmalt ,  J. A. C. Clyburne ,  A. H. Cowley, R. Pyati Chem. Commun., 1997, 981-982

  9. A new phosphanido imidazolium zwitterion P.K.Majhi,G.Schnakenburg, Z.Kelemen,L.Nyulaszi, D. Gates,R.Streubelto be published

  10. Abnormal N-heterocyclic carbenes (aNHC) ΔpKa=9 P. L. Arnold , S. PearsonCoord Chem Rev2007251, 596–609 O. Schuster, L. Yang, H. G. Raubenheimer, M. Albrecht Chem. Rev. 2009,109, 3445–3478S. Gründemann, A. Kovacevic, M. Albrecht, J. Faller, R. H. Crabtree,Chem. Commun. 2001, 2274-2275. E. Aldeco-Perez, A. J. Rosenthal, B. Donnadieu, P. Parameswaran, G. Frenking, G. Bertrand, Science2009326, 556-557

  11. Tautomers

  12. Phosphino carbenes J. I. Bates, P. Kennepohl, D. P. Gates, Angew. Chem.2009, 121, 10028 – 10031; Angew. Chem. Int. Ed. 2009, 48, 9844 –9847. D. Mendoza-Espinosa, B. Donnadieu, G. Bertrand, J. Am. Chem. Soc.2010, 132, 7264 –7265.

  13. Tautomers

  14. The nitrogen analogue ? • A. Danopoulos, K. Y. Monakhov, P. Braunstein, Chem. Eur. J. 2013, 19, 450 – 455

  15. The silicon analogue A. P. Singh, P. P. Samuel, K. C. Mondal, H. W. Roesky, N. S. Sidhu, B. Dittrich,Organometallics, 2013, 32 , 354–357

  16. The silicon analogue A. P. Singh, P. P. Samuel, K. C. Mondal, H. W. Roesky, N. S. Sidhu, B. DittrichOrganometallics, 2013, 32 , 354–357

  17. Main goals -relative stability -Dual reactivity?

  18. Results

  19. Relative stability R=H X B3LYP/6-311+G**

  20. X=O, S, NH, PH, CH2, NH2

  21. Relative stability R=H X B3LYP/6-311+G**

  22. X=O, S

  23. Relative stability R=H X B3LYP/6-311+G**

  24. X=CR2, SiR2

  25. Relative stability R=H X B3LYP/6-311+G**

  26. X=PR2. NR2 Possible chemical equilibrium?

  27. Aromaticity, NICS(0) R=H X B3LYP/6-311+G**

  28. Aromaticity, NICS(1) R=H X B3LYP/6-311+G**

  29. Pniktogen group R1 R2 B3LYP/6-311+G**

  30. Substituent effect B3LYP/6-311+G**

  31. Summary -possible tautomeric equilibrium-dual reactivity X=PR

  32. Acknowledgments Financial support from New SzechenyiPlan TAMOP-4.2.2/B-10/1-2010-0009 is gratefully acknowledged

  33. Rotamers P-phenyl bond length 1.852 Å 1.788 Å P-imidazolium-unit bond length 1.839 Å 1.806 Å Relative stability B3LYP/6-311+G** 0.0 2.1 B97D/6-311+G** 0.0 0.7 M06-2X/6-311+G** 0.0 0.9

  34. Further methods

  35. Difference beetwen the Si an C analogue

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