Chemistry - An Asian Journal
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In conclusion, the [MnV(N)(CN)4]2/IO4 catalytic system is
unusually efficient in the oxidation of various alkanes. Excellent
yields of >95 % and TON of 3000 are obtained. The active
intermediate is proposed to be the Mn(VII) nitrido oxo species,
[MnVII(N)(O)(CN)4]2, which can also be generated using H2O2 or
Ce(IV) as oxidant. The observed higher product yields and
F. Montanari, S. Quici, J. Chem. Soc., Chem. Commun. 1990, 24, 1794
– 1796; c) S. Ménage, M. N. Collomb-Dunand-Sauthier, C. Lambeaux,
M. Fontecave, J. Chem. Soc., Chem. Commun. 1994, 16, 1885 – 1886;
d) G. B. Shul’pin, G. V. Nizova, Yu. N. Kozlov, I. G. Pechenkina, New. J.
Chem. 2002, 26, 1238 – 1245; e) K. Nehru, S. J. Kim, I. Y. Kim, M. S.
Seo, Y. Kim, S. J. Kim, J. Kim, W. Nam, Chem. Commun. 2007, 44,
4623 – 4625; f) G. B. Shul’pin, M. G. Matthes, V. B. Romakh, M. I. F.
Barbosa, J. L. T. Aoyagi, D. Mandelli, Tetrahedron 2008, 64, 2143 –
2152.
TONs than using H2O2 is probably because IO4 is thermally
more stable and less susceptible to decomposition by trace
metals. This work further demonstrates that [MnV(N)(CN)4]2 is a
versatile catalyst that can utilize a variety of oxidants for the
efficient functionalization of unactivated C-H bonds under mild
conditions.
[7]
[8]
a) J. P. Collman, H. Tanaka, R. T. Hembre, J. I. Brauman, J. Am. Chem.
Soc. 1990, 112, 3689 – 3690; b) A. Sorokin, A. Robert, B. Meunier, J.
Am. Chem. Soc. 1993, 115, 7293 – 7299; c) Z. Fang, R. Breslow,
Bioorg. Med. Chem. Lett. 2005, 15, 5463 – 5466.
a) D. Mohajer, R. Tayebee, H. Goudarziafshar, J. Chem. Res. Synop.
1998, 12, 822 – 823; b) B. Bahramian, V. Mirkhani, S. Tangestaninejad,
M. Moghadam, J. Mol. Catal. A: Chem. 2006, 244, 139 – 145; c) B.
Bahramian, V. Mirkhani, M. Moghaam, S. Tangestaninejad, Appl. Catal.
A: General 2006, 301, 169 – 175; d) V. Mirkhani, M. Moghadam, S.
Tangestaninejad, H. Kargar, Appl. Catal. A: General 2006, 303, 221 –
229.
Acknowledgements
The work described in this paper was supported by Hong Kong
University Grants Committee Area of Excellence Scheme
(AoE/P-03-08), the Research Grants Council of Hong Kong
(CityU 101713), the Shenzhen Science and Technology
Research Grant (JCYJ20150601102053067) and the Shenzhen
Research Institute, City University of Hong Kong.
[9]
J. Bendix, K. Meyer, T. Weyhermüller, E. Bill, N. Metzler-Nolte, K.
Wieghardt, Inorg. Chem. 1998, 37, 1767 – 1775.
[10] L. Ma, Y. Pan, W. L. Man, H. K. Kwong, W. W. Y. Lam, G. Chen, K. C.
Lau, T. C. Lau, J. Am. Chem. Soc. 2014, 136, 7680 – 7687.
[11] H. K.; Kwong, P. K. Lo, K. C. Lau, T. C. Lau, Chem. Commun. 2011, 47,
4273 – 4275.
[12] L. Ma, Q. Wang, W. L. Man, H. K. Kwong, C. C. Ko, T. C. Lau, Angew.
Chem. Int. Ed. 2015, 54, 5246 – 5249.
Keywords: alkane oxidation • C-H activation • periodate •
catalysis • manganese nitrido complex
[13] a) M. Zhou, U. Hintermair, B. G. Hashiguchi, A. R. Parent, S. M. Hashmi,
M. Elimelech, R. A. Periana, G. W. Brudvig, R. H. Crabtree,
Organometallics, 2013, 32, 957 – 965; b) M. Moghadam, V. Mirkhani, S.
Tangestaninejad, I. Mohammdpoor-Baltork, H. Kargar, J. Mol. Catal. A:
Chem. 2008, 288, 116 – 124; c) B. C. Bales, P. Brown, A. Dehestani, J.
M. Mayer, J. Am. Chem. Soc. 2005, 127, 2832 – 2833; d) A. J. Bailey,
W. P. Griffith, A. J. P. White, D. J. Williams, J. Chem. Soc., Chem.
Commun. 1994, 16, 1833 – 1834; e) Z. M. Hu, H. X. Du, C. F. Leung, H.
J. Liang, T. C. Lau, Ind. Eng. Chem. Res. 2011, 50, 12288 – 12292; f)
P. Tan, H. K. Kwong, T. C. Lau, Chem. Commun. 2015, 51, 12189 –
12192.
[1]
[2]
K. I. Goldberg, A. S. Goldman, Activation and Functionalization of C-H
Bonds, ACS Symposium Series 885; American Chemical Society:
Washington, DC, 2004.
a) R. Breslow, X. Zhang, Y. Huang, J. Am. Chem. Soc. 1997, 119, 4535
– 4536; b) R. Breslow, Y. Huang, X. Zhang, Y. Yang, Proc. Natl. Acad.
Sci. U. S. A. 1997, 94, 11156 – 11158; c) Y. Yang, R. Breslow, Angew.
Chem. Int. Ed. 2000, 39, 2692 – 2694; d) Z. Fang, R. Breslow, Org. Lett.
2006, 8, 251 – 254.
[3]
[4]
a) C. A. Quintana, R. A. Assink, J. Shelnutt, Inorg. Chem. 1989, 28,
3421 – 3425; b) B. R. Cook, T. J. Reinert, K. S. Suslick, J. Am. Chem.
Soc. 1986, 108, 7282 – 7286.
[14]
a) D. C. Nonhebel, J. M. Tedder, J. C. Walton, Radicals, Cambridge
University Press: Cambridge, 1979; b) A. Marchaj, D. G. Kelley, A.
Bakac, J. H. Espenson, J. Phys. Chem. 1991, 95, 4440 – 4441.
a) C. M. Che, V. K. Y. Lo, C. Y. Zhou, J. S. Huang, Chem. Soc. Rev.
2011, 40, 1950 – 1975; b) R. I. Khusnutdinov, A. R. Bayguzina, U. M.
Dzhemilev, Russ. J. Org. Chem. 2012, 48, 309 – 348; c) E. P. Talsi, K.
P. Brylialov, Coord. Chem. Rev. 2012, 256, 1418 – 1434.
A. Company, J. Lloret, L. Gómez, M. Costas, in Alkane C–H Activation
by Single-Site Metal Catalysis, P. J. Pérez, Ed.; Springer: Dordrecht,
2012; pp 176 – 185.
[15] a) W. J. Song, M. S. Seo, S. D. George, T. Ohta, R. Song, M. Kang, T.
Tosha, T. Kitagawa, E. Solomon, W. Nam, J. Am. Chem. Soc. 2007,
129, 1268 – 1277; b) T. C. Lau, J. Y. Wang, K. W. M. Siu, R.
Guevremont, J. Chem. Soc., Chem. Commun. 1994, 12, 1487 – 1488.
[16] J. L. McLain, J. Lee, J. T. Groves, in Biomimetic Oxidations Catalyzed by
Transition Metal Complexes, Meunier, B., Ed.; Imperial College Press:
London, 2000; pp 91 – 169.
[5]
[6]
a) P. Battioni, J. P. Renaud, J. F. Bartoli, D. Mansuy, J. Chem. Soc.,
Chem. Commun. 1986, 4, 341 – 343; b) S. Banfi, A. Maiocchi, A. Moggi,
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