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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

Author:
Gutierrez, Osvaldo, Aubé, Jeffrey, Tantillo, Dean J.
Source:
Journal of organic chemistry 2012 v.77 no.1 pp. 640-647
ISSN:
1520-6904
Subject:
chemical reactions, methodology, moieties, nitrogen, organic chemistry, organic compounds, 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 N₂-loss/shift of the alkyl group antiperiplanar to the N₂ 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.
Agid:
5498705