The heterocyclization pattern was directed to dihydrotriazines by increasing amidine excess up to 4–5 equivs. The dihydrotriazine ring was constructed from two acetimidamide molecules and one steroid molecule via the nucleophilic attack of two amidine molecules on the formyl group. The reaction of acetimidamide with potassium carbonate in DMF produced heterosteroids 4a–c containing the dihydrotriazine substituent at the 16-C or 2-C position of the steroid core in 29–32% yields. The structural assignments for all compounds 3a–f and 4a–c were confirmed by 2D NMR (1H-1H COSY, 13C-1H HMBC, and 13C-1H HSQC, see Supplementary Material) techniques and HRMS.