OPTIMIZING AND UNDERSTANDING SELECTIVITY USING MOLECULAR DESCRIPTORS

Due to their capacity for delineating hydrophobic, electronic, and steric effects, classical physical organic molecular descriptors, such as logP, Hammett, Taft, or Charton parameters are used for elucidating reaction mechanisms. However, often each of these parameters alone cannot account for the intricate molecular interactions invoked in modern synthetic chemistry. Experimental inquiry, complemented by multivariate physical organic analysis, can bridge this gap and enable the study and optimization of increasingly complex systems. In this talk, I will present a novel data analysis strategy based on infrared molecular vibrations, and several applications thereof. This recently disclosed approach enables the prediction of chemical outcomes and the study of reaction mechanisms in cases where structural effects are not intuitive or additive.

Milo, A.; Neel, A. J.; Toste, F. D.; Sigman, M. S., A data-intensive approach to mechanistic elucidation applied to chiral anion catalysis. Science 2015, 347, 737-743.

• Perspective: Lu, T.; Wheeler, S. E. Harnessing weak interactions for enantioselective catalysis. Science 2015, 347, 719-720.
• Research highlight: Hennessy, J., Asymmetric synthesis: Catalysis exposed. Chem. 2015, 7, 270-270.
• Highlighted: University of Utah press release, C&E News, Phys.org.

Milo, A.; Sigman M. S., Appling Mathematical Modeling to the Analysis of Catalytic Reaction Outcomes: A Historical Perspective. In Seminars in Organic Synthesis: XXXIX “A. Corbella” International Summer School. SCI: 2014, 15-35.

Milo, A.; Bess, E. N.; Sigman, M. S., Interrogating selectivity in catalysis using molecular vibrations. Nature 2014, 507, 210-214.

• Highlighted: University of Utah press release, C&E News, Phys.org.
• Selected as one of the biggest Chemicals Technology stories of 2014.