Asymmetric nitrogen—41: Stereochemistry of bicyclic 1,2-cis-diaziridines

The twisting of 5- and 6-membered rings in bicyclic cis-diaziridines—1,5-diazabicyclo [3.1.0]hexanes 12–17 and l,6-diazabicyclo[4.1.0]heptane 18—is a rapid process in the time scale of ¹H- and ¹³C-NMR even at -80°. According to the ¹H- and ¹³C-NMR spectra, 1,5-diazabicyclo [3.1.0]hexanes 12,13,15a,15b and 16a,16b do, exist mostly in the boat form ; only the introduction of endo substituents into position 3 or 6 leads to the population of the chair, as is the case with 14 and 17. 2,4-Dialkyl substituted 1,5-diaza- and 1,3,5-triazabicyclo[3.1.0]hexanes are formed via a transition cyclization state similar in its geometry to the initial chair-shaped N-chlorodi(tri)azanes.