Mechanism of the acid-promoted intramolecular schmidt reaction: theoretical assessment of the importance of lone pair-cation, cation-, and steric effects in controlling regioselectivity. Academic Article uri icon


  • The mechanism of the acid-catalyzed intramolecular Schmidt reaction of 2-azidopropylcyclohexanones was studied using density functional theory (primarily M06-2X). The reaction was found to proceed through rapid formation of azidohydrin intermediates followed by rate-determining concerted N(2)-loss/shift of the alkyl group antiperiplanar to the N(2) leaving group. For cases where steric, lone pair-cation, and cation- effects have been invoked previously as regiocontrol elements, the origins and magnitudes of these effects have been examined theoretically.

published proceedings

  • J Org Chem

author list (cited authors)

  • Gutierrez, O., Aub, J., & Tantillo, D. J.

citation count

  • 38

complete list of authors

  • Gutierrez, Osvaldo||AubĂ©, Jeffrey||Tantillo, Dean J

publication date

  • January 2012