Journal of the American Chemical Society
Communication
(b) Tenn, W. J., III; Young, K. J. H.; Oxgaard, J.; Nielsen, R. J.;
Goddard, W. A., III; Periana, R. A. Organometallics 2006, 25, 5173.
(9) (a) Kloek, S. M.; Heinekey, D. M.; Goldberg, K. I. Angew. Chem.,
Int. Ed. 2007, 46, 4736. (b) Hanson, S. K.; Heinekey, D. M.; Goldberg,
K. I. Organometallics 2008, 27, 1454. (c) Bercaw, J. E.; Hazari, N.;
Labinger, J. A. Organometallics 2009, 28, 5489.
(10) Hashiguchi, B. G.; Young, K. J. H.; Yousufuddin, M.; Goddard,
W. A., III; Periana, R. A. J. Am. Chem. Soc. 2010, 132, 12542.
(11) (a) Cundari, T. R.; Grimes, T. V.; Gunnoe, T. B. J. Am. Chem.
Soc. 2007, 129, 13172. (b) Ess, D. H.; Nielsen, R. J.; Goddard, W. A.,
III; Periana, R. A. J. Am. Chem. Soc. 2009, 131, 11686. (c) Ess, D. H.;
Goddard, W. A., III; Periana, R. A. Organometallics 2010, 29, 6459.
(d) Ess, D. H.; Gunnoe, T. B.; Cundari, T. R.; Goddard, W. A., III;
Periana, R. A. Organometallics 2010, 29, 6801.
(12) Brown, S. N.; Mayer, J. M. J. Am. Chem. Soc. 1996, 118, 12119.
(13) (a) Alsters, P. L.; Boersma, J.; van Koten, G. Organometallics
1993, 12, 1629. (b) Alsters, P. L.; Teunissen, H. T.; Boersma, J.; Spek,
A. L.; van Koten, G. Organometallics 1993, 12, 4691. (c) Singh, A.;
Agarwala, A.; Kamaraj, K.; Bandyopadhyay, D. Inorg. Chim. Acta 2011,
372, 295.
(14) (a) Matsunaga, P. T.; Hillhouse, G. L.; Rheingold, A. L. J. Am.
Chem. Soc. 1993, 115, 2075. (b) Matsunaga, P. T.; Mavropoulos, J. C.;
Hillhouse, G. L. Polyhedron 1995, 14, 175. (c) Koo, K.; Hillhouse, G.
L.; Rheingold, A. L. Organometallics 1995, 14, 456.
C−H activation by a metal alkoxide complex, transfer and
insertion of oxygen into the metal−hydrocarbyl bond, and
regeneration of the oxygen transfer agent. There are few
examples of oxygen atom insertion into metal−carbon bonds,
and understanding of the various pathways for oxygen
insertion, which might be used to design strategies to facilitate
reactions, is limited. The results of the combined experimental
and computational studies herein are consistent with flavins
acting as organocatalysts for the insertion of an oxygen atom
into the Re−CH3 bond of MTO with rate enhancements up to
600-fold. These results suggest that the existing repertoire of
organic BV catalysts might be leveraged as a strategy in the
development of oxygen atom insertions into metal−hydro-
carbyl bonds that can be incorporated into catalyic partial
oxidations of hydrocarbons.
ASSOCIATED CONTENT
* Supporting Information
■
S
General experimental procedures and characterization details.
This material is available free of charge via the Internet at
(15) (a) Abu-Omar, M. M.; Hansen, P. J.; Espenson, J. H. J. Am.
Chem. Soc. 1996, 118, 4966. (b) Espenson, J. H.; Tan, H.; Mollah, S.;
Houk, R. S.; Eager, M. D. Inorg. Chem. 1998, 37, 4621. (c) Wang, W.-
D.; Espenson, J. H. J. Am. Chem. Soc. 1998, 120, 11335. (d) Pestovsky,
O.; van Eldik, R.; Huston, P.; Espenson, J. H. J. Chem. Soc., Dalton
Trans. 1995, 133. (e) Yamazaki, S.; Espenson, J. H.; Huston, P. Inorg.
Chem. 1993, 32, 4683. (f) Adolfsson, H.; Coperet, C.; Chiang, J. P.;
́
Yudin, A. K. J. Org. Chem. 2000, 65, 8651. (g) Herrmann, W. A.;
Fischer, R. W.; Rauch, M. U.; Scherer, W. J. Mol. Catal. 1994, 86, 243.
AUTHOR INFORMATION
Corresponding Author
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was solely supported as part of the Center for
Catalytic Hydrocarbon Functionalization, an Energy Frontier
Research Center funded by the U.S. Department of Energy,
Office of Science, Office of Basic Energy Sciences, under Award
DE-SC0001298.
(h) Coper
1565. (i) Coper
Sharpless, K. B. J. Org. Chem. 1998, 63, 1740.
́
et, C.; Adolfsson, H.; Sharpless, K. B. Chem. Commun. 1997,
́
et, C.; Adolfsson, H.; Khuong, T.-A. V.; Yudin, A. K.;
(16) (a) Conley, B. L.; Ganesh, S. K.; Gonzales, J. M.; Tenn, W. J.,
III; Young, K. J. H.; Oxgaard, J.; Goddard, W. A., III; Periana, R. A. J.
Am. Chem. Soc. 2006, 128, 9018. (b) Gonzales, J. M.; Distasio, R., Jr.;
Periana, R. A.; Goddard, W. A., III; Oxgaard, J. J. Am. Chem. Soc. 2007,
129, 15794.
(17) Bischof, S. M.; Cheng, M.-J.; Nielsen, R. J.; Gunnoe, T. B.;
Goddard, W. A., III; Periana, R. A. Organometallics 2011, 30, 2079.
(18) (a) Figg, T. M.; Cundari, T. R.; Gunnoe, T. B. Organometallics
2011, 30, 3779. (b) Figg, T. M.; Webb, J. R.; Cundari, T. R.; Gunnoe,
T. B. J. Am. Chem. Soc. 2012, 134, 2332.
REFERENCES
■
(1) (a) Oyama, S. T. In Mechanisms in Homogeneous and
Heterogeneous Epoxidation Catalysis; Oyama, S. T., Ed.; Elsevier:
Amsterdam, 2008; Chapter 1, pp 3−99. (b) Backvall, J.-E. Modern
Oxidation Methods, 2nd ed.; Wiley-VCH: Weinheim, Germany, 2010.
(2) Olah, G. A.; Goeppert, A.; Prakash, G. K. S. Beyond Oil and Gas:
The Methanol Economy, 2nd ed.; Wiley-VCH: Weinheim, Germany,
2009.
(3) (a) Shilov, A. E.; Shul’pin, G. B. Chem. Rev. 1997, 97, 2879.
(b) Stahl, S. S.; Labinger, J. A.; Bercaw, J. E. Angew. Chem., Int. Ed.
1998, 37, 2180.
(4) (a) Lersch, M.; Tilset, M. Chem. Rev. 2005, 105, 2471.
(b) Labinger, J. A. J. Mol. Catal. A: Chem. 2004, 220, 27. (c) Weinberg,
D. R.; Labinger, J. A.; Bercaw, J. E. Organometallics 2007, 26, 167.
(d) Conley, B. L.; Tenn, W. J., III; Young, K. J. H.; Ganesh, S. K.;
Meier, S. K.; Ziatdinov, V. R.; Mironov, O.; Oxgaard, J.; Gonzales, J.;
Goddard, W. A., III; Periana, R. A. J. Mol. Catal. A: Chem. 2006, 251, 8.
(e) Periana, R. A.; Bhalla, G.; Tenn, W. J., III; Young, K. J. H.; Liu, X.
Y.; Mironov, O.; Jones, C. J.; Ziatdinov, V. R. J. Mol. Catal. A: Chem.
2004, 220, 7.
̈
(19) (a) Kamerbeek, N. M.; Janssen, D. B.; van Berkel, W. J. H.;
Fraaije, M. W. Adv. Synth. Catal. 2003, 345, 667. (b) Mihovilovic, M.
D. Curr. Org. Chem. 2006, 10, 1265. (c) Torres Pazmino, D. E.;
̃
Winkler, M.; Glieder, A.; Fraaije, M. W. J. Biotechnol. 2010, 146, 9.
(d) Leisch, H.; Morley, K.; Lau, P. C. K. Chem. Rev. 2011, 111, 4165.
(20) (a) Mazzini, C.; Lebreton, J.; Furstoss, R. J. Org. Chem. 1996,
61, 8. (b) Murahashi, S.-I.; Ono, S.; Imada, Y. Angew. Chem., Int. Ed.
2002, 41, 2366. (c) Imada, Y.; Iida, H.; Murahashi, S. I.; Naota, T.
Angew. Chem., Int. Ed. 2005, 44, 1704.
̌
́ ́ ̌ ́ ́
(21) Menova, P.; Kafka, F.; Dvorakova, H.; Gunnoo, S.; Sanda, M.;
Cibulka, R. Adv. Synth. Catal. 2011, 353, 865.
(22) Tomasi, J.; Cammi, R.; Mennucci, B. Int. J. Quantum Chem.
1999, 75, 783.
(23) Abu-Omar, M. M.; Appelman, E. H.; Espenson, J. H. Inorg.
Chem. 1996, 35, 7751.
(5) Webb, J. R.; Bolano, T.; Gunnoe, T. B. ChemSusChem 2011, 4,
̃
37.
(24) Holm, R. H.; Donahue, J. P. Polyhedron 1993, 12, 571.
(25) Lee, S. C.; Holm, R. H. Inorg. Chim. Acta 2008, 361, 1166.
(6) Conner, D.; Jayaprakash, K. N.; Cundari, T. R.; Gunnoe, T. B.
Organometallics 2004, 23, 2724.
(7) (a) Feng, Y.; Lail, M.; Barakat, K. A.; Cundari, T. R.; Gunnoe, T.
B.; Petersen, J. L. J. Am. Chem. Soc. 2005, 127, 14174. (b) Feng, Y.;
Lail, M.; Foley, N. A.; Gunnoe, T. B.; Barakat, K. A.; Cundari, T. R.;
Petersen, J. L. J. Am. Chem. Soc. 2006, 128, 7982.
(8) (a) Tenn, W. J., III; Young, K. J. H.; Bhalla, G.; Oxgaard, J.;
Goddard, W. A., III; Periana, R. A. J. Am. Chem. Soc. 2005, 127, 14172.
12923
dx.doi.org/10.1021/ja3054139 | J. Am. Chem. Soc. 2012, 134, 12920−12923