Mechanistic study of stereoselectivity in azoalkane denitrogenations

Since 1965, the stereoselectivity in azoalkane denitrogenation has attracted much attention in both synthetic organic chemistry and physical organic chemistry. In this paper, a short review of the recent findings on the mechanism underlying the fascinating stereoselectivity in azoalkane denitrogenation is presented. The two types of singlet diradicals, i.e. the puckered and planar conformations, were found to play important roles in the stereoselectivity in the photochemical denitrogenation of cyclic azoalkanes. The presence of the puckered singlet diradical, which is the third isomer in homolysis, resolves the mechanistic puzzle reported so far for the stereoselectivity in azoalkane denitrogenations.