The first example of 1,3-dipolar cycloaddition reactions of C-aryl (or hetaryl)-N-phenylnitrones to monosubstituted ylidene malononitriles and 4-benzylidene-2-phenyl-oxazol-5(4H)-one is described. The reaction of C-(4-(dimethylamino)phenyl)-N-phenyl-nitrone (1a) with 2-(4-substituted-benzylidene)malononitriles 2a, b in dry toluene, in the absence of catalyst, at reflux temperature furnished the novel cycloadducts 2-(3-aryl-2-phenyl-2,3-dihydro-1,2,4-oxadiazol-5-yl)-3-(4-methoxyphenyl)acrylonitriles 3a, b. Refluxing C-aryl (or hetaryl)-N-phenylnitrones 1b–i with 2-(4-methoxy-benzylidene)malononitrile (2a) in dry toluene, in the absence of catalyst, gave the unexpected 2-cyano-3-(4-methoxyphenyl)-acrylamide (5), as the sole product. On the other hand, refluxing 4-benzylidene-2-phenyloxazol-5(4H)-one (7) with an equimolar amount of C-aryl (or hetaryl)-N-phenyl-nitrones 1a–c, f–i in absolute EtOH afforded the previously unknown 5-anilino-4-benzoyl-2-phenyloxazole (10), as the only isolable product. The resulting products were formed with a high degree of regio- and stereoselectivity. Quantum chemical calculations were performed to verify stereoselectivity of the studied reaction. A mechanistic proposal is presented to rationalize the formation of these products.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian09, Revision D.01, Gaussian, Inc., Wallingford, CT (USA) 2009.
Zeitschrift für Naturforschung B is an international scientific journal which publishes original papers, microreviews, and letters from all areas of inorganic chemistry, solid state chemistry, coordination chemistry, molecular chemistry, and organic chemistry.