Ru-Catalyzed C-H Activation

Wang cheng ming

2013.2.25

2

Two popular catalysts’ price contrast

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4

Ru3(CO)12

RuH2(CO)(PPh3)3

[RuCl2(C6H6)]2

[RuCl2(p-cymene)]2

[RuCl2(cod)]n

RuCl3.xH2O

RuCl2(PPh3)3

Common used Ru catalyst

5

Prepare

Ru(C5H8O2)2CO, H2

MeOH, 165 oCRu3(CO)12

RuCl3. 3H2OMeOH, reflux

nPPh3 RuCl2(PPh)3

RuCl3 EtOH, reflux[RuCl2C6H6]2

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Ru-catalyzed C-H activation

Cross oxidative coupling

Directing C-H activation

Summary

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Oxidative Cross Coupling

HAr XAr'[Ru]

Oxidative couplingAr'Ar

X=H, Halo...

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, 5841.

alkylation

11Lee, 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, 5782.

cyclization

14

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

15

Proposed mechanism:

16

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

Zip reaction

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Directing C-H activation

H

DG

[Ru] Ru

DG

DG

R

DG

R

R

18

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

Arylation using ArX

19

Oi, S.; Sakai, K.; Inoue, Y. Org. Lett. 2005, 7, 4009.

Ackermann, L. Org. Lett. 2005, 7, 3123.

Reactivity

20Arockiam, 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, 1783.

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.

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Other additives: KOAc, 1-AdCO2H, MesCO2H, Ad2POH

Additives

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

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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.

Application

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Ackermann, L.; Novak, P.; Vicente, R.; Pirovano, V.; Potukuchi, H. K. Synthesis 2010, 2245.

Homocoupling

27

Oi, S.; Tanaka, Y.; Inoue, Y. Organometallics 2006, 25, 4773.

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

29Ackermann, L.; Vicente, R.; Althammer, A. Org. Lett. 2008, 10, 2299.

Broad substrates scope

30

N

NN

N

HN

N

S

NO

N

N N

N

R

N

OMe

Other directing groups:

31Ackermann, L.; Novak, P.; Vicente, R.; Hofmann, N. Angew. Chem., Int. Ed. 2009, 48, 6045.

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, 7325.

Alkylation using alcohol

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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, 19298.

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Proposed SEAr mechanism:

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Alkenylation

39

COOH

H

Yu, 2010

OHH

Yu, 2010

O

H

Glorius, 2011

HN

HO

Leeuwen, 2002

N

H

Shi, 2007

S

O

ONHC6F5

H

Yu, 2011

O

OEt

H

Chang, 2011

NH

O

OMe

Wang, 2011

O

H

HJeganmohan, 2012

Sii-Pr

OH

i-Pr

H

2011, Ge

NN

N

Our report

NN

H

2011,Dixneuf

Various directing groups:

40

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

Carboxylic acid

Phenyl pyrazole

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

Amide

42Padala, K.; Jeganmohan, M. Org. Lett. 2011, 13, 6144.

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.

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

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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, 6379.

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.

50Kakiuchi, F.; Sato, T.; Tsujimoto, T.; Yamauchi, M.; Chatani, N.; Murai, S. Chem. Lett. 1998, 27, 1053.

selectivity

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

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Indene formation mechanism:

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Other reaction

Thirunavukkarasu, V. S.; Ackermann, L. Org. Lett. 2012, 14, 6206.

Wang, L.; Ackermann, L. Org. Lett. 2013, 15, 176.

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Future may focus on:

React at other C-H site other than ortho.

Catalytic sp3 C-H activation.

Aerobic oxidations .

Other new reaction.

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Further reviews

Rh: Satoh, T.; Miura, M. Chem. Eur. J. 2010, 16, 11212.

Ru: Kozhushkov, S. I.; Ackermann, L. Chem. Sci., 2012, 3, 886.

Ackermann, L. Acc. Chem. Res., 2013, ASAP, DOI: 10.1021/ar3002798.

Lutz Ackermann

http://www.ackermann.chemie.uni-goettingen.de/