The iminium intermediate generated by the reaction between a secondary amine and cinnamaldehyde was reacted with N‐isocyanimino‐triphenylphosphorane in the presence of benzoic acid derivatives to form the corresponding iminophosphorane intermediate, whose intramolecular aza‐Wittig reaction led to disubstituted 1,3,4‐oxadiazole derivatives. The syntheses were completed under neutral conditions at room temperature to give excellent yields. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:315–321, 2012; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.21013