A novel type of heterocyclization reaction involving the [3+2] cycloaddition of N,N-dialkylamino-substituted thioisomunchnones with azodicarboxylates gives rise to 1,2,4-triazine derivatives after a selective fragmentation pathway of the transient cycloadducts. The X-ray analysis of 7 accounts for the fate of this particular transformation. An asymmetric version using chiral carbohydrate-based thioisomunchnones has also been disclosed. (C) 1999 Elsevier Science Ltd. All rights reserved.