Catalyst-free synthesis of tetrahydropyrimidines via formal [3+3]-cycloaddition of imines with 1,3,5-hexahydro-1,3,5-triazines.

A practical and environmentally benign synthesis of poly-substituted tetrahydropyrimidines from readily available starting materials has been developed. This process features an unprecedented intermolecular formal [3+3]-annulation of imines and 1,3,5-hexahydro-1,3,5-triazines under catalyst-free conditions. Importantly, differing from previous transformations, the 1,3,5-triazines are firstly utilized as formal 1,3-dipoles in cycloaddition reactions.