Reaction of 2-aminopyridines with formaldehyde and electron rich alkenes permits synthesis of pyridopyrimidines by formation of imines and subsequent addition to the alkenes in a formal aza Diels Alder reaction. The structure of the cyclic amidine products is confirmed by single crystal X-ray analysis on a neutral amidine isolated from an aminopyridine substituted with an electron withdrawing trifluoromethyl group and of a trifluoroacetate salt of an amidine obtained from 2-aminopyridine, formaldehyde and indene. These structural studies permit the regio- and stereo-chemical outcome of these addition to be defined mid compared with related processes. Copyright (C) 1996 Published by Elsevier Science Ltd