The diastereoselective synthesis of a series of 1-oxo-1,2,3,3a,4,7a-hexahydro-pyrano[3,4- c]pyrrole-4-carboxylic acid ethyl esters via an oxo Diels–Alder reaction is described. Ab initio calculations predicted the products of the exo cycloaddition to be the thermodynamic products while the products resulting from the endo cycloaddition were predicted to be the kinetic products. The calculations were born out by experimental data.