Microwave irradiation facilitated the synthesis of 4-arylthio-3-oxazolin-5-ones from ethyl cyanoformate, thiophenol, and cyclic ketones. Subsequent decarboxylation and in situ [3+ 2] cycloaddition provided novel 2, 3, 4, 5-tetrahydro-1H-pyrrolo [1, 2-c][1, 3] diazepine scaffolds after a spontaneous retro-Mannich domino reaction.