ru-catalyzed c-h activation
DESCRIPTION
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. - PowerPoint PPT PresentationTRANSCRIPT
Ru-Catalyzed C-H Activation
Wang cheng ming
2013.2.25
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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...
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Weissman, H.; Song, X.; Milstein, D. J. Am. Chem. Soc., 2001,123, 337–338.
Oxidative coupling C-H activation
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Tan, S. T.; Teo, Y. C.; Fan, W. Y. J. Organomet. Chem. 2012, 58, 708.
alkenylation
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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.
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acylation
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Yi, C. S.; Yun, S. Y.; Guzei, I. A. J. Am. Chem. Soc. 2005, 127, 5782.
cyclization
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Yi, C. S.; Yun, S. Y. J. Am. Chem. Soc. 2005, 127, 17000.
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Proposed mechanism:
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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
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Oi, S.; Fukita, S.; Hirata, N.; Watanuki, N.; Miyano, S.; Inoue, Y. Org. Lett. 2001, 3, 2579.
Arylation using ArX
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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.
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Oi, S.; Ogino, Y.; Fukita, S.; Inoue, Y. Org. Lett. 2002, 4, 1783.
Selectivity
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Oi, S.; Aizawa, E.; Ogino, Y.; Inoue, Y. J. Org. Chem. 2005, 70, 3113.
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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
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Oi, S.; Tanaka, Y.; Inoue, Y. Organometallics 2006, 25, 4773.
Oi, S.; Sato, H.; Sugawara, S.; Inoue, Y. Org. Lett. 2008, 10,1823.
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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
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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
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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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Acylation reaction
Kochi, T.; Tazawa, A.; Honda, K.; Kakiuchi, F. Chem. Lett. 2011, 40, 1018.
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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.
37
Proposed SEAr mechanism:
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Alkenylation
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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
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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
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Hashimoto, Y.; Ueyama, T.; Fukutani, T.; Hirano, K.; Satoh,T.; Miura, M. Chem. Lett. 2011, 40, 1165.
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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.
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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/