Joel Smolanoff

Photocyclodimerization of arylazirenes to 1,3-diazabicyclo[3,1,0]hex-3-enes

Irradiation of arylazirenes gives 1,3-diazabicyclo[3,1,0]hex-3-enes via 1,3-dipolar addition of an initially generated nitrile ylide on to a ground state arylazirene molecule.

Rationale for the direction of regioselectivity in the photocycloaddition of arylazirines

The photoconversion of substituted arylazirines (1) into methoxyimines (3) proceeds via a nitrile ylide intermediate (2); deuterium labelling results indicate that the electron density is highest on the disubstituted carbon atom of the nitrile ylide.