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An unprecedented version of the Biginelli reaction using an unprotected aldose as a biorenewable aldehyde component and 2-phenyl-1,3-oxazol-5-one as a novel active methylene building block with urea/thiourea is reported. The reaction is cerium(III)catalyzed, expeditious, and effected under solvent-free microwave irradiation conditions to yield diastereoselectively, iminosugar-annulated polyfuntionalized perhydropyrimidines via ring transformation of an isolable intermediate followed by cyclodehydration.