ACS Catalysis
Research Article
(5) (a) Yamaguchi, K.; Mori, K.; Mizugaki, T.; Ebitani, K.; Kaneda, K.
J. Am. Chem. Soc. 2000, 122, 7144. (b) Choi, E.; Lee, C.; Na, Y.;
Chang, S. Org. Lett. 2002, 4, 2369. (c) Yamaguchi, K.; Mizuno, N.
Angew. Chem., Int. Ed. 2002, 41, 4538. (d) Zhan, B.-Z.; White, M. A.;
Sham, T.-K.; Pincock, J. A.; Doucet, R. J.; Rao, K. V. R.; Robertson, K.
N.; Cameron, T. S. J. Am. Chem. Soc. 2003, 125, 2195. (e) Ebitani, K.;
Ji, H.-B.; Mizugaki, T.; Kaneda, K. J. Mol. Catal. A: Chem. 2004, 212,
161. (f) Mizuno, N.; Yamaguchi, K. Catal. Today 2008, 132, 18.
(g) Yamaguchi, K.; Kim, J. W.; He, J.; Mizuno, N. J. Catal. 2009, 268,
343. (h) Yu, H.; Fu, X.; Zhou, C.; Peng, F.; Wang, H.; Yang, J. Chem.
Commun. 2009, 2408. (i) Yasu-eda, T.; Kitamura, S.; Ikenaga, N.;
Miyake, T.; Suzuki, T. J. Mol. Catal. A: Chem. 2010, 323, 7. (j) Costa,
V. V.; Jacinto, M. J.; Rossi, L. M.; Landers, R.; Gusevskaya, E. V. J.
(C28H25ClF6N4O3PRu): C, 45.02; H, 3.37; N, 7.50. Found C,
44.79; H, 3.41; N, 7.50.
1d: The compound was obtained as a green solid (92 mg,
27%). ESI-MS: m/z = 592{M-PF6}+. Anal. Calcd. for 1b
(C27H18ClF9N4PRu): C, 44.00; H, 2.46; N, 7.60. Found C,
43.82; H, 2.60; N, 7.60.
Oxidative Dehydrogenation of 2-Phenylimidazoline.
A mixture of 2-phenylimidazoline (65.8 mg, 0.45 mmol),
ruthenium complex (4.5 × 10−3 mmol), K2CO3 (62.2 mg, 0.45
mmol), and mesitylene (31.3 μL, 0.225 mmol) in methanol (3
mL) was stirred at 55 °C under a balloon pressure of O2 (1
1
atm). The yield and conversion were determined by H NMR
Catal. 2011, 282, 209. (k) Marko,
́
I. E.; Giles, P. R.; Tsukazaki, M.;
spectroscopy using mesitylene as an internal standard.
Chelle-Regnaut, I.; Urch, C. J.; Brown, S. M. J. Am. Chem. Soc. 1997,
́
́
119, 12661. (l) Csjernyik, G.; Ell, A. H.; Fadini, L.; Pugin, B.; Backvall,
̈
ASSOCIATED CONTENT
́
■
J.-E. J. Org. Chem. 2002, 67, 1657. (m) Zsigmond, A.; Notheisz, F.;
S
* Supporting Information
Csjernyik, G.; Backvall, J.-E. Top. Catal. 2002, 19, 119. (n) Arita, S.;
̈
Koike, T.; Kayaki, Y.; Ikariya, T. Chem.Asian J. 2008, 3, 1479.
General experimental and characterization procedures, compu-
tational details, crystallographic data, and spectroscopic data.
This material is available free of charge via the Internet at
(o) Johnston, E. V.; Karlsson, E. A.; Tran, L.-H.; Åkermark, B.;
Backvall, J.-E. Eur. J. Org. Chem. 2010, 1971. (p) Guo, H.; Liu, W.-D.;
̈
Yin, G. Appl. Organomet. Chem. 2011, 25, 836. (q) Lee, M.; Chang, S.
Tetrahedron Lett. 2000, 41, 7507. (r) Komiya, N.; Nakae, T.; Sato, H.;
Naota, T. Chem. Commun. 2006, 4829. (s) Nakamura, Y.; Egami, H.;
Matsumoto, K.; Uchida, T.; Katsuki, T. Tetrahedron 2007, 63, 6383.
(t) Mizoguchi, H.; Uchida, T.; Ishida, K.; Katsuki, T. Tetrahedron Lett.
2009, 50, 3432. (u) Zhang, W.-H.; Chien, S. W.; Hor, T. S. A. Coord.
Chem. Rev. 2011, 255, 1991.
AUTHOR INFORMATION
■
Corresponding Author
Notes
(6) (a) Taketoshi, A.; Koizumi, T.; Kanbara, T. Tetrahedron Lett.
2010, 51, 6457. (b) Aiki, S.; Taketoshi, A.; Kuwabara, J.; Koizumi, T.;
Kanbara, T. J. Organomet. Chem. 2011, 696, 1301. (c) Taketoshi, A.;
Beh, X. N.; Kuwabara, J.; Koizumi, T.; Kanbara, T. Tetrahedron Lett.
2012, 53, 3573. (d) Koizumi, T.; Kanbara, T. Bull. Jpn. Soc. Coord.
Chem. 2010, 56, 14.
(7) (a) Parmentier, M.; Gros, P.; Fort, Y. Tetrahedron 2005, 61, 3261.
(b) Kim, S.-H.; Rieke, R. D. Tetrahedron Lett. 2009, 50, 5329.
(c) Billingsley, K. L.; Buchwald, S. L. Angew. Chem., Int. Ed. 2008, 47,
4695.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This research was supported by the Cooperative Research
Program of the “Network Joint Research Center for Materials
and Devices”. The authors are grateful to the Chemical Analysis
Center of University of Tsukuba for X-ray diffractional studies,
elemental analyses, and NMR spectroscopy.
(8) (a) Hadadzadeh, H.; DeRosa, M. C.; Yap, G. P. A.; Rezvani, A.
R.; Crutchley, R. J. Inorg. Chem. 2002, 41, 6521. (b) Bomben, P. G.;
Robson, K. C. D.; Sedach, P. A.; Berlinguette, C. P. Inorg. Chem. 2009,
48, 9631.
(9) Since the molecular orbitals (MO) and their levels in complex 1a
have been reported by Berlinguette et al. (ref 8b) as a Ru(II) complex,
those of the complexes 1b−d were also calculated as a Ru(II) complex,
respectively.
REFERENCES
■
(1) (a) Bellina, F.; Cauteruccio, S.; Rossi, R. Tetrahedron 2007, 63,
4571. (b) Voss, M. E.; Beer, C. M.; Mitchell, S. A.; Blomgren, P. A.;
Zhichkin, P. E. Tetrahedron 2008, 64, 645. (c) Ishihara, M.; Togo, H.
Synlett 2006, 227. (d) de la Hoz, A.; Díaz-Ortiz, A.; Mateo, M.; del,
C.; Moral, M.; Moreno, A.; Elguero, J.; Foces-Foces, C.; Rodríguez, M.
́
́ ́
L.; Sanchez-Migallon, A. Tetrahedron 2006, 62, 5868. (e) Mohammad-
(10) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci,
B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H.
P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.;
Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima,
T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.;
Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin,
K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.;
Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega,
N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.;
Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.;
Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.;
Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.;
poor-Baltork, I.; Zolfigol, M. A.; Abdollahi-Alibeik, M. Tetrahedron
Lett. 2004, 45, 8687. (f) Nicolaou, K. C.; Mathison, C. J. N.;
Montagnon, T. J. Am. Chem. Soc. 2004, 126, 5192. (g) Anastassiadou,
M.; Baziard-Mouysset, G.; Payard, M. Synthesis 2000, 1814.
(h) Amemiya, Y.; Miller, D. D.; Hsu, F.-L. Synth. Commun. 1990,
20, 2483. (i) Hughey, J. L.; Knapp, S.; Schugar, H. Synthesis 1980, 489.
(j) Mohammadpoor-Baltork, I.; Zolfigol, M. A.; Abdollahi-Alibeik, M.
Synlett 2004, 2803. (k) Kargar, H.; Moghadam, M.; Mirkhani, V.;
Tangestaninejad, S.; Mohammadpoor-Baltork, I.; Naghipour, M.
Polyhedron 2011, 30, 1463. (l) Kargar, H. Inorg. Chem. Commun.
2011, 14, 863.
(2) Recent reviews of catalytic oxidation with molecular oxygen:
(a) Punniyamurthy, T.; Velusamy, S.; Iqbal, J. Chem. Rev. 2005, 105,
2329. (b) Schultz, M. J.; Sigman, M. S. Tetrahedron 2006, 62, 8227.
(c) Parmeggiani, C.; Cardona, F. Green Chem. 2012, 14, 547.
̈
Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.;
Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09,
Revision A.1; Gaussian, Inc.: Wallingford, CT, 2009.
(11) Ka = [1a·Im2]/([1a][Im]2). For the determination of Ka values,
see the Supporting Information.
(12) Ishihara, M.; Togo, H. Tetrahedron 2007, 63, 1474.
(13) Constable, E. C.; Thompson, A. M. W. C.; Tocher, D. A.;
Daniels, M. A. M. New J. Chem. 1992, 16, 855.
(d) Schumperli, M. T.; Hammond, C.; Hermans, I. ACS Catal. 2012,
̈
2, 1108.
(3) The aerobic oxidation of 2-imidazolines has recently been
reported: (a) Haneda, S.; Okui, A.; Ueba, C.; Hayashi, M. Tetrahedron
2007, 63, 2414. (b) Huang, Y.; Zu, X.; Wu, F.; Xu, J.; Wu, X.; Yao, H.
Tetrahedron 2012, 68, 3123.
(4) Taketoshi, A.; Tsujimoto, A.; Maeda, S.; Koizumi, T.; Kanbara, T.
ChemCatChem 2010, 2, 58.
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dx.doi.org/10.1021/cs300811w | ACS Catal. 2013, 3, 812−816