Ru-Catalyzed C-H Activation Wang cheng ming

2 Two popular catalysts’ price contrast

3

4 Common used Ru catalyst

5 Prepare

6 Ru-catalyzed C-H activation  Cross oxidative coupling  Directing C-H activation  Summary

7 Oxidative Cross Coupling

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

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

10 Onodera, G.; Imajima, H.; Yamanashi, M.; Nishibayashi, Y.; Hidai, M.; Uemura, S. Organometallics 2004, 23, alkylation

11 Lee, D.-H.; Kwon, K.-H.; Yi, C. S. Science 2011, 333, 1613.

12 acylation

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

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

15 Proposed mechanism:

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

17 Directing C-H activation

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

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

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

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

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

23 Ackermann, L.; Born, R.; Vicente, R. ChemSusChem 2009, 2, 546.

24 Other additives: KOAc, 1-AdCO 2 H, MesCO 2 H, Ad 2 POH Additives Arockiam, P. B.; Fischmeister, C.; Bruneau, C.; Dixneuf, P. H. Angew. Chem., Int. Ed. 2010, 49, 6629.

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

26 Ackermann, L.; Novak, P.; Vicente, R.; Pirovano, V.; Potukuchi, H. K. Synthesis 2010, Homocoupling

27 Oi, S.; Tanaka, Y.; Inoue, Y. Organometallics 2006, 25, Oi, S.; Sato, H.; Sugawara, S.; Inoue, Y. Org. Lett. 2008, 10,1823.

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

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

30 Other directing groups:

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

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

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

34

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

36 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,

37 Proposed S E Ar mechanism:

38 Alkenylation

39 Various directing groups:

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

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

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

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

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

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

46 Cyclization

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

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

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

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

51 Yi, C. S.; Lee, D. W. Organometallics 2010, 29, 1883.

52

53 Indene formation mechanism:

54 Other reaction Thirunavukkarasu, V. S.; Ackermann, L. Org. Lett. 2012, 14, Wang, L.; Ackermann, L. Org. Lett. 2013, 15, 176.

55 Future may focus on:  React at other C-H site other than ortho.  Catalytic sp 3 C-H activation.  Aerobic oxidations.  Other new reaction.

56 Further reviews Rh: Satoh, T.; Miura, M. Chem. Eur. J. 2010, 16, Ru: Kozhushkov, S. I.; Ackermann, L. Chem. Sci., 2012, 3, 886. Ackermann, L. Acc. Chem. Res., 2013, ASAP, DOI: /ar Lutz Ackermann