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"
Davis, R. L.; Tantillo, D. J. Curr. Org. Chem. 2010,14, 1561-1577: "Theoretical Studies on Pentadienyl Cation Electrocyclizations," invited review for special issue on Molecular Simulations in Organic Chemistry.
Harrison, J. G.; Tantillo, D. J. J. Molec. Model. 2013, 19, 1981-1984: "Role of Gold in a Complex Cascade Reaction Involving Two Electrocyclization Steps," invited for special issue on Quitel 2011.
Nguyen, Q. N. N.; Xia, K. T.; Zhang, Y.; Chen, N.; Morimoto, M.; Pei, X.; Ha, Y.; Guo, J.; Yang, W.; Wang, L.-P.; Bergman, R. G.; Raymond, K. N.; Toste, F. D.; Tantillo, D. J. J. Am. Chem. Soc. 2022, 144, 11413-11424: "Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages"
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.
Phillip 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.
Jason G. Harrison and Dean J. Tantillo: "Mechanistic Insight into an Unusual Gold(I)-Catalyzed Nazarov Cyclization." Poster presented by Jason Harrison at the at the Bradford Borge Weekend, University of California, Davis, CA, February 19-20, 2010.
Jason G. Harrison and Dean J. Tantillo: "Mechanistic Insight into an Unusual Gold(I)-Catalyzed Nazarov Cyclization." Poster presented by Jason Harrison at the at the Graduate Student Recruiting Weekend, University of California, Davis, CA, March 18-19, 2010.
Jason G. Harrison and Dean J. Tantillo: "Unusual Gold(I)-Catalyzed N-Nazarov Cyclization." Lecture presented by Jason Harrison at the 239th ACS National Meeting, San Francisco, CA, March 21-25, 2010; paper ORGN 37.
Jason G. Harrison and Dean J. Tantillo: "Theoretical Investigation of an Unusual Gold(I) Catalyzed Imino-Nazarov Cyclization." Poster presented by Jason Harrison at the R. Bryan Miller Symposium, UC Davis, Davis, CA, April 8-9, 2010.
Jason G. Harrison and Dean J. Tantillo: "Theoretical Investigation of an Unusual Gold(I) Catalyzed Imino-Nazarov Cyclization." Poster presented by Jason Harrison at the 33rd Reaction Mechanisms Conference, University of Massachusetts, Amherst, MA, June 23-26, 2010.
