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A facile regioselective synthesis of substituted pyrido[1,2-a]pyrimidinium salts 5a-f from α-oxoketene N,S-acetals 2a-f, 6a-d from N,N-acetals 3a-d, 7b-c from N,O-acetals 4b-c, and 8a-c from N,S-acetals 2a-c is described. The scope and mechanisms of these reactions have been investigated.

Intramolecular cycloannulation of α-oxoketene N,N-,N,S- and N,O-acetals: synthesis of novel pyrido[1,2-a]pyrimidinium tetrafluoroborates