The first example of an exo-camphorylsulfonyloxaziridine 4a was prepar
ed by m-CPBA oxidation of camphor imine 9. This surprising result is d
ue to the conformation of the imine which apparently prevents attack o
f the peracid from the endo direction. Similar oxidations of all other
camphorsulfonylimines result in the endo-oxaziridine exclusively. Asy
mmetric oxidation of sulfides to sulfoxides and the alpha-hydroxylatio
n of enolates by 4 can be interpreted in terms of open transition stat
es where nonbonded interactions are minimized. These results support e
arlier conclusions and predictions of the stereoselectivity and mechan
isms of molecular recognition by the N-sulfonyloxaziridine class of ox
idizing reagents.