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Ru-Catalyzed C-H Activation

Ru-Catalyzed C-H Activation. Wang cheng ming. 2013.2.25. Two popular catalysts’ price contrast. Common used Ru catalyst. Prepare. Ru-catalyzed C-H activation. Cross oxidative coupling Directing C-H activation Summary. Oxidative Cross Coupling.

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Ru-Catalyzed C-H Activation

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  1. Ru-Catalyzed C-H Activation Wang cheng ming 2013.2.25

  2. Two popular catalysts’ price contrast

  3. Common used Ru catalyst

  4. Prepare

  5. Ru-catalyzed C-H activation • Cross oxidative coupling • Directing C-H activation • Summary

  6. OxidativeCross Coupling

  7. Oxidative coupling C-H activation Weissman, H.; Song, X.; Milstein, D. J. Am. Chem. Soc., 2001,123, 337–338.

  8. alkenylation Tan, S. T.; Teo, Y. C.; Fan, W. Y. J. Organomet. Chem.2012, 58, 708.

  9. alkylation Onodera, G.; Imajima, H.; Yamanashi, M.; Nishibayashi, Y.; Hidai, M.; Uemura, S. Organometallics2004, 23, 5841.

  10. Lee, D.-H.; Kwon, K.-H.; Yi, C. S. Science2011, 333, 1613.

  11. acylation

  12. cyclization Yi, C. S.; Yun, S. Y.; Guzei, I. A. J. Am. Chem. Soc.2005, 127, 5782.

  13. Yi, C. S.; Yun, S. Y. J. Am. Chem. Soc.2005, 127, 17000.

  14. Proposed mechanism:

  15. Zip reaction Youn, S. W.; Pastine, S. J.; Sames, D. Org. Lett.2004, 6, 581.

  16. Directing C-H activation

  17. Arylation using ArX Oi, S.; Fukita, S.; Hirata, N.; Watanuki, N.; Miyano, S.; Inoue, Y. Org. Lett.2001, 3, 2579.

  18. Reactivity Oi, S.; Sakai, K.; Inoue, Y. Org. Lett.2005, 7, 4009. Ackermann, L. Org. Lett.2005, 7, 3123.

  19. Arockiam, P. B.; Fischmeister, C.; Bruneau, C.; Dixneuf, P. H. Angew. Chem., Int. Ed. 2010, 49, 6629.

  20. Selectivity Oi, S.; Ogino, Y.; Fukita, S.; Inoue, Y. Org. Lett.2002, 4, 1783.

  21. Oi, S.; Aizawa, E.; Ogino, Y.; Inoue, Y. J. Org. Chem.2005, 70, 3113.

  22. Ackermann, L.; Born, R.; Vicente, R. ChemSusChem2009, 2, 546.

  23. Additives Other additives: KOAc, 1-AdCO2H, MesCO2H, Ad2POH Arockiam, P. B.; Fischmeister, C.; Bruneau, C.; Dixneuf, P. H. Angew. Chem., Int. Ed. 2010, 49, 6629.

  24. Application Ouellet, S. G.; Roy, A.; Molinaro, C.; Angelaud, R.; Marcoux, J. F.; O’Shea, P. D.; Davies, I. W. J. Org. Chem.2011, 76, 1436.

  25. Homocoupling Ackermann, L.; Novak, P.; Vicente, R.; Pirovano, V.; Potukuchi, H. K. Synthesis2010, 2245.

  26. Oi, S.; Tanaka, Y.; Inoue, Y. Organometallics2006, 25, 4773. Oi, S.; Sato, H.; Sugawara, S.; Inoue, Y. Org. Lett.2008, 10,1823.

  27. Cheap catalyst Luo, N.; Yu, Z. K. Chem.Eur. J.2010, 16, 787. Seki, M. Acs Catal.2011, 1, 607.

  28. Broad substrates scope Ackermann, L.; Vicente, R.; Althammer, A. Org. Lett.2008, 10, 2299.

  29. Other directing groups:

  30. Alkylation using sp3 RX Ackermann, L.; Novak, P.; Vicente, R.; Hofmann, N. Angew. Chem., Int. Ed.2009, 48, 6045.

  31. Ackermann, L.; Novak, P. Org. Lett.2009, 11, 4966.

  32. Alkylation using alcohol Lee, D.-H.; Kwon, K.-H.; Yi, C. S. J. Am. Chem. Soc.2012, 134, 7325.

  33. Acylation reaction Kochi, T.; Tazawa, A.; Honda, K.; Kakiuchi, F. Chem. Lett.2011, 40, 1018.

  34. Saidi, O.; Marafie, J.; Ledger, A. E. W.; Liu, P. M.; Mahon, M. F.; Kociok-Kohn, G.; Whittlesey, M. K.; Frost, C. G. J. Am. Chem. Soc.2011, 133, 19298.

  35. Proposed SEAr mechanism:

  36. Alkenylation

  37. Various directing groups:

  38. Carboxylic acid Phenyl pyrazole Ackermann, L.; Pospech, J. Org. Lett.2011, 13, 4153. Arockiam, P. B.; Fischmeister, C.; Bruneau, C.; Dixneuf, P. H. Green Chem.2011, 13, 3075.

  39. Amide Ackermann, L.; Wang, L.; Wolfram, R.; Lygin, A. V. Org. Lett.2012, 14, 728.

  40. Aldehyde Ketone Padala, K.; Jeganmohan, M. Org. Lett.2011, 13, 6144.

  41. Oxime ether Li, B.; Ma, J. F.; Wang, N. C.; Feng, H. L.; Xu, S. S.; Wang, B. Q. Org. Lett. 2012, 14, 736.

  42. Using alkyne Cheng, K.; Yao, B. B.; Zhao, J. L.; Zhang, Y. H. Org. Lett.2008,10, 5309.

  43. Hashimoto, Y.; Hirano, K.; Satoh, T.; Kakiuchi, F.; Miura, M. Org. Lett.2012, 14, 2058.

  44. Cyclization

  45. Hashimoto, Y.; Ueyama, T.; Fukutani, T.; Hirano, K.; Satoh,T.; Miura, M. Chem. Lett.2011, 40, 1165.

  46. Ackermann, L.; Lygin, A. V.; Hofmann, N. Angew. Chem., Int. Ed.2011, 50, 6379. Ackermann, L.; Lygin, A. V.; Hofmann, N. Org. Lett.2011, 13, 3278.

  47. Ackermann, L.; Wang, L.; Lygin, A. V. Chem. Sci.2012, 3, 177. Chinnagolla, R. K.; Jeganmohan, M. Eur. J. Org. Chem.2012, 2012, 417.

  48. selectivity Kakiuchi, F.; Sato, T.; Tsujimoto, T.; Yamauchi, M.; Chatani, N.; Murai, S. Chem. Lett. 1998, 27, 1053.

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