A new simple method for the synthesis of 2‐thioxo‐1,2,3,4,4a,10b‐hexahydro‐5H‐chromeno[4,3‐d]pyrimidin‐5‐ones via acid‐catalyzed condensation of Biginelli products with 1,3‐benzenediols was developed. The diastereoselectivity of this reaction was studied in details. A convenient work‐up procedure providing the major (4R*,4aS*,10bR*) diastereomer from the reaction mixture was found.
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