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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

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journal contribution
posted on 06.01.2012, 00:00 by Osvaldo Gutierrez, Jeffrey Aubé, Dean J. Tantillo
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.

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