In collaboration with the Sarpong group at UC Berkeley, we have used density functional theory calculations to compare the reactivity of a variety of dienyl ketones in Lewis acid promoted Nazarov cyclizations (4-electron electrocyclizations of oxygen-substituted pentadienyl cations). The facility of these reactions was shown to be dependent upon the presence or absence of alkyl groups at various positions on the diene substructure. In particular, A(1,3) strain promotes these cyclizations.
Subsequently, we have expanded ourt studies to a variety of other interesting Nazarov and related reactions.
Marcus, A. P; Lee, A. S.; Davis, R. L.; Tantillo, D. J.; Sarpong, R. Angew. Chem. Int. Ed. 2008, 47, 6379-6383: "Pronounced Steric Effects of Substituents in the Nazarov Cyclization of Aryl Dienyl Ketones"
Jason C. Harrison and Dean J. Tantillo: "Mechanistic Insight into and Unusual Gold(I)-Catalyzed Nazarov Cyclization." Poster presented by Jason Harrison at the SYLICCO.09 Symposium, Davis, CA, July 23, 2009.
Philip P. Painter and Dean J. Tantillo: "Eclipsing Transition States and Their Role in Chiral Imidazoline Racemization." Poster presented by Phil Painter at the SYLICCO.09 Symposium, Davis, CA, July 23, 2009.
