1. Home ›
  2. Research

Asymmetric Catalysis

People

Asymmetric catalysis is the use of a chiral catalyst that favors the formation of one stereoisomer. A chiral feature biases the formation of one stereoisomer through interactions at the transition state. Identification of chiral catalyst and reaction conditions often requires empircal optimization. C-CAS seeks to integrate data chemistry to inform the selection of optimal catalysts and bypass time-consuming traditional reaction development strategies.

Publications

  • Gensch T, dos Passos Gomes G, Friederich P, Peters E, Gaudin T, Pollice R, et al. A Comprehensive Discovery Platform for Organophosphorus Ligands for Catalysis. J. Am. Chem. Soc. 2022, 144 ASAP  https://pubs.acs.org/doi/full/10.1021/jacs.1c09718

  • Cadge, J., Hart, S.D., Walroth, R.C., Sigman, M.S.; Mack, K., 2025. Bisphosphine ligand conformer selection to enhance descriptor database representation: improving statistical modelling outcomes. Chem. Sci. 2025, 16, 20473-20485 https://doi.org/10.1039/D5SC04691B

  • Ortiz, K.; Dotson, J.; Robinson, D. J.; Sigman, M. S.; Karimov, R. R. “Catalyst-controlled enantioselective and regiodivergent addition of aryl boron nucleophiles to N-alkyl nicotinate salts,” J. Am. Chem. Soc. 2023, 145, 21,11781-11788. https://doi.org/10.1021/jacs.3c03048

  • Gensch, T.; Smith, S.R; Colacot, T.J.; Timsina, Y.; Xu, G.; Glasspoole, B.W.; Sigman, M.S, Design and Application of a Screening Set for Monophosphine Ligands in Metal Catalysis. ACS Catal. 2022. 12, 13, 7773-7780.  https://doi.org/10.1021/acscatal.2c01970

  • Wiesler, S., Sennari, G., Popescu, M.V., Gardner, K.E., Aida, K., Paton, R.S., Sarpong, R. Late-stage benzenoid-to-troponoid skeletal modification of the cephalotanes exemplified by the total synthesis of harringtonolide. Nature Communications. 2024, 15:4125. doi: 10.1038/s41467-024-48586-6.

  • Ickes, A.R., Liles, J.P., Borlinghaus, N., Henle, J., Swiatowiec, R., Prakash Kaushik, N., Braje, W.M., Harper, K.C., Shekhar, S. and Sigman, M.S., 2025. Leveraging Data Science to Elucidate Ligand Features for Pd-Catalyzed Enantioretentive N-Arylations of Cyclic α-Substituted Amines in Aqueous Media. J. Am. Chem. Soc. 2025, 147, ASAP https://doi.org/10.1021/jacs.5c07224

  • Heafner, E.D., Smith, A.L., Craescu, C.V., Raymond, K.N., Berman, R.G., Toste, F.D. Probing enantioinduction in confined chiral spaces through asymmetric oxime reductions. Chem, Online now. Dec 23, 2024. https://doi.org/10.1016/j.chempr.2024.11.006

  • Smith, A.L., Toste, F.D. Stereoselective Generalizations over Diverse Sets of Chiral Acids Enabled by Buried Volume. J. Am. Chem. Soc. 2026, 148, 2792-2800. https://doi.org/10.1021/jacs.5c20342

  • Williams, W.L.; Zeng, L.; Gensch, T.; Sigman, M.S.; Doyle, A.G.; Anslyn, E. V. The Evolution of Data-Driven Modeling in Organic Chemistry.  ACS Cent. Sci. 2021, 7, 1622-1637. https://doi.org/10.1021/acscentsci.1c00535

  • Gallarati, S., Bucci, E.M., Doyle, A.G. et al. Transferable enantioselectivity models from sparse data. Nature (2026). https://doi.org/10.1038/s41586-026-10239-7

  • Hardy, M.A.; Cooke, J.H.; Feng, Z.; Noda, K.; Kerschgens, I.; Massey, L.A.; Tantillo, D.J.; Sarpong, R. Unified Synthesis of 2-Isocyanoallopupukeanane and 9-Isocyanopupukeanane through a "Contra-biosynthetic" Rearrangement. Angew. Chem. Int. Ed. 2024, 63. https://doi.org/10.1002/anie.202317348

Experimental Chemistry

Computational Chemistry

Computer Science

Broader Impacts