Regio- and stereoselective 1,3-dipolar cycloaddition reactions of C-aryl (or hetaryl)-N-phenylnitrones to monosubstituted ylidene malononitriles and 4-benzylidene-2-phenyloxazol-5(4H)-one

Abstract

Abstract 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.