Highly functionalized oxazinanes are efficiently prepared through urea-catalyzed formal [3 + 3] cycloaddition reactions of nitrones and nitrocyclopropane carboxylates. The reaction system is general with respect to both the nitrocyclopropane carboxylates and nitrones enabling the preparation of a large family of oxazinanes, typically in high yield. This method affords access to enantioenriched oxazinane products through chirality transfer from enantioenriched nitrocyclopropane carboxylates.