Regioselective Ring Expansion of 2,4-Diiminoazetidines via Cleavage of C-N and C(sp3)-H Bonds: Efficient Construction of 2,3-Dihydropyrimidinesulfonamides

A highly regioselective base-mediated ring expansion of 2,4-diiminoazetidines via cleavage of C-N and C(sp(3))-H bonds is achieved for the first time to afford efficiently 2,3-dihydropyrimidinesulfonamides. The mechanism of the ring expansion via tandem 4 pi electrocyclic ring-opening/1,5-H shift/6 pi electrocydic ring-closing is well confirmed by the trapping experiments of two key intermediates and deuterium labeling studies.