Unexpected and facile bridgehead substitution in 5,6,7,8,9,10-hexahydro-5,9-methano-pyrimido[4,5-]azocin-4(3)-ones

Abstract Condensation of 2,6-diamino-4(3 H )-pyrimidinone with 2-cyclohexen-1-one gives a tricyclic product resulting from Michael addition followed by intramolecular hemiaminal formation. A methodology has been developed for reductive removal of the bridgehead hydroxyl group.