Alison J. Frontier

Alison J. Frontier

Associate Professor of Chemistry

Ph.D. 1999, Columbia University

Synthetic Organic Chemistry

The final test of the value of any bond-forming method is its application to the synthesis of complex target molecules. Conversely, target-oriented synthetic research can lead to important methodological discoveries. A natural product often contains a common structural motif, so that studying synthetic routes often leads to the development of a strategy applicable to an entire class of molecules with similar structure. During the planning stages, difficulties encountered often represent common synthetic problems, identifying gaps in current technology. A synthetic project provides a context for methodological study and can lead to the discovery of new chemistry with wider applicability.

Professor Frontier's research program is devoted to the planning and execution of syntheses of biologically and structurally interesting natural products. A particular focus is the use of transition metal catalysis to rapidly construct complex molecular architecture from simple starting materials. Transition metal complexes present in catalytic proportions can often perform extremely specific transformations in the presence of complex functionality. The development of such reactions has the potential to change current trends in synthetic strategy.

Selected Publications

Malona, J. M., Cariou, K., Spencer, W. T., Frontier, A. J.  "Total Synthesis of (±)-Rocaglamide via Oxidation-Initiated Nazarov Cyclization,"  J. Org. Chem.  2012771891-1908.
Leboeuf, D., Huang, J., Gandon, V., Frontier, A. J.  "Using Nazarov Electrocyclization to Stage Chemoselective [1,2]-Migrations: Stereoselective Synthesis of Functionalized Cyclopentenones,"  Angewandte Chem. Int. Ed.  20115010981-10985.
Vaidya, T., Eisenberg, R., Frontier, A. J.  "Catalytic Nazarov Cyclization: The State of the Art,"  Chem. Cat. Chem.  201131531-1548.
Brooks, J. L., Caruana, P. A., Frontier, A. J.  "Conjugate Addition-Initiated Nazarov Cyclization,"  J. Am. Chem. Soc.  201113312454-12457.
Trost, B. M., Frontier, A. J., Thiel, O. R., Yang, H., Dong, G.  "Total Synthesis of Bryostatins: The Development of Methodology for the Atom-Economic and Stereoselective Synthesis of the Ring C Subunit,"  Chem. Eur. J.  2011179762-9776.
Huang, J., Leboeuf, D., Frontier, A. J.  "Understanding the Fate of the Oxyallyl Cation following Nazarov Electrocyclization: Sequential Wagner-Meerwwin Migrations and the Synthesis of Spirocyclic Cyclopentenones,"  J. Am. Chem. Soc.  20111336307-6317.
Vaidya, T., Manbeck, G. R., Chen, S., Frontier, A. J.  "Divergent Reaction Pathways of a Cationic Intermediate: Rearrangement and Cyclization of 2-Substituted Furyl and Benzofuryl Enones Catalyzed by Iridium(III),"  J. Am. Chem. Soc.  20111333300-3303.
Spencer, W. T., Levin, M. D., Frontier, A. J.  "Oxidation-Initiated Nazarov Cyclization of Vinyl Alkoxyallenes,"  Org. Lett.  201113414-417.
Zhang, J., Vaidya, T., Brennessel, W. W., Frontier, A. J., Eisenberg, R.  "Dicationic Palladium(II) Complexes as Active Lewis Acid Catalysts for Polarized Nazarov Cyclization,"  Organometalics  2010293341-3349.
Vaidya, T., Atesin, A. C., Herrick, I. R., Frontier, A. J., Eisenberg, R.  "A Highly Reactive Dicationic Iridium(III) Catalyst for the Polarized Nazarov Cyclization Reaction,"  Angewandte Chem. Int. Ed.  2010493363-3366.
Atesin, A. C., Zhang, J., Vaidya, T., Brennessel, W. W., Frontier, A. J., Eisenberg, R.  "Synthesis, Characterization, and Catalytic Properties of New Electrophilic Iridium(III) Complexes Containing the (R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl Ligand,"  Org. Lett.  2010494331-4342.
Ciesielski, J., Canterbury, D. P., Frontier, A. J.  "β-Iodoallenolates as Springboards for Annulation Reactions,"  Org. Lett.  2009114374-4377.
Canterbury, D. P., Herrick, I. R., Um, J., Houk, K. N., Frontier, A. J.  "A torquoselective extrusion of isoxazoline N-oxides. Application to the synthesis of aryl vinyl and divinyl ketones for Nazarov cyclization,"  Tetrahedron  2009653165-3179.
Malona, J. M., Cariou, K., Frontier, A. J.  "Nazarov Cyclization Initiated by Peracid Oxidation: The Total Synthesis of (±)-Rocaglamide,"  J. Am. Chem. Soc.  20091317560-7561.
Bitar, A. Y., Frontier, A. J.  "Formal Synthesis of Roseophilin,"  Org. Lett.  20091149-52.
He, W., Herrick, I. R., Atesin, T. A., Caruana, P. A., Kellenberger, C. A., Frontier, A. J.  "Polarizing the Nazarov Cyclization: The Impact of Dienone Substitution Pattern on Reactivity and Selectivity,"  J. Am. Chem. Soc.  20081301003-1011.
He, W., Huang, J., Frontier, A. J.  "Total Synthesis of (±)-Merrilactone A,"  J. Am. Chem. Soc.  2008130300-308.
Jiang, C., Frontier, A. J.  "Stereoselective Synthesis of Pyrrolidine Derivatives via Reduction of Substituted Pyrroles,"  Org. Lett.  200794939-4942.
Huang, J., Frontier, A. J.  "Development of a Nazarov Cyclization/ Wagner-Meerwein Rearrangement Sequence for the Stereoselective Synthesis of Spirocycles,"  J. Am. Chem. Soc.  20071298060-8061.
Malona, J. A., Colbourne, J. M., Frontier, A. J.  "A General Method for the Catalytic Nazarov Cyclization of Heteroaromatic Compounds,"  Org. Lett.  200685661-5664.
Janka, M., He, W., Haedicke, I. E., Fronczek, F. R., Frontier, A. J., Flaschenriem, C., Eisenberg, R.  "Tandem Nazarov Cyclization-Michael Addition Sequence Catalyzed by an Ir(III) Complex,"  J. Am. Chem. Soc.  20061285312-5313.
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Professor Frontier's Contact Information...

Office: Hutchison 414
Phone: (585) 275-2568

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