An unprecedented cascade Michael/cyclization reaction of 4‐chromanone derivatives, aldehydes, and 2‐cyanothioacetamide was presented for the preparation of distinctive 2‐amino‐4‐aryl‐5H‐chromeno[4,3‐b]pyridine‐3‐carbonitriles promoted by ammonium acetate. The optimized reaction conditions were used for the synthesis of 2‐amino‐4‐aryl‐5H‐chromeno[4,3‐b]pyridine‐3‐carbonitrile derivatives in medium to high yields. The synthetic method features a convenient operational process, easy access to raw material as well as high atom economy.

A convenient and straightforward cascade Michael/cyclization reaction of 1‐alkylpiperidin‐4‐ones, acyl acetonitriles, and aldehydes was proposed for the construction of significant 8‐aryl‐6‐aryl‐1,2,3,4‐tetrahydroisoquinoline‐5,7‐dicarbonitriles promoted by DBU, and various 8‐aryl‐6‐aryl‐1,2,3,4‐tetrahydroisoquinoline‐5,7‐dicarbonitrile derivatives were produced in medium to high yields. The methodology features a simple operation process, accessible raw material, and high atomic economy.