title: Mechanism of the acid-promoted intramolecular schmidt reaction: theoretical assessment of the importance of lone pair-cation, cation-π, and steric effects in controlling regioselectivity.
abstract: 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-π effects have been invoked previously as regiocontrol elements, the origins and magnitudes of these effects have been examined theoretically.
authors: Department of Chemistry, University of California at Davis, Davis, California 95616, United States.
authors: Osvaldo
authors: O
authors: Gutierrez
authors: Jeffrey
authors: J
authors: Aubé
authors: Dean J
authors: DJ
authors: Tantillo
mesh_terms: D000143:Acids / Q000737:chemistry*; D002384:Catalysis; D002412:Cations / Q000737:chemistry*; D003512:Cyclohexanones / Q000737:chemistry*; D008958:Models, Molecular; D008962:Models, Theoretical; D015394:Molecular Structure; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D000143:Acids; D002412:Cations; D003512:Cyclohexanones