Mechanism
Chemical mechanisms are the detailed step-by-step pathways by which chemical reactions occur. Understanding reaction mechanisms is crucial for the prediction of reaction outcomes and for informing the development of more accurate models. Within C-CAS, we strive to elucidate mechanistic information about chemical transformations by combining experimental and computational approaches such as DFT, coupled cluster, ML force fields (ex. AIMNET), linear regression, and transition state calculations.
Publications
Bartholomew, G.L.; Kraus, S.L.; Karas, L.J.; Carpaneto, F.; Bennett, R.; Sigman, M.S.; Yeung, C.S.; Sarpong, R. “14N to 15N Isotopic Exchange of Nitrogen Heteroaromatics through Skeletal Editing” ChemRxiv 2023 .10.26434/chemrxiv-2023-30dtw
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
Luchini, Guilian, and Robert Paton. "Bottom-up Atomistic Descriptions of Top-Down Macroscopic Measurements: Computational Benchmarks for Hammett Electronic Parameters." ACS Phys. Chem Au, 2024
Matthews, A.D., Peters, E., Debenham, J.S., Gao, Q., Nyamiaka, M.D., Pan, J., Zhang, L.K., Dreher, S.D., Krska, S.W., Sigman, M.S. and Uehling, M.R., 2023. Cu Oxamate-Promoted Cross-Coupling of α-Branched Amines and Complex Aryl Halides: Investigating Ligand Function through Data Science. ACS Catalysis, 13(24), 16195-16206. doi https://doi.org/10.1021/acscatal.3c04566
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
Silva, J. D. J.; Bartalucci, N.; Jelier, B.; Grosslight, S.; Gensch, T.; Schünemann, C.; Müller, B.; Kamer, P. C.; Copéret, C.; Sigman, M. S., Development and Molecular Understanding of a Pd-catalyzed Cyanation of Aryl Boronic Acids Enabled by High-Throughput Experimentation and Data Analysis. Helv. Chim. Acta 2021 e2100200. https://doi.org/10.1002/hlca.202100200
Crawford, J.M.; Gensch, T.; Sigman, M.S.; Elward, J.M.; Steves, J.E. Impact of Phosphine Featurization Methods in Process Development. Org. Proc. Res. Dev. 2022, 26, 4, 1115-1123 https://doi.org/10.1021/acs.oprd.1c00357
Gallegos, L.C.; Luchini, G.; St John, P.C.; Kim, S.; Paton, R.S. Importance of Engineered and Learned Molecular Representations in Predicting Organic Reactivity, Selectivity, and Chemical Properties Acc. Chem. Res. 2021, 54, 4, 827-836. https://pubs.acs.org/doi/10.1021/acs.accounts.0c00745
Newman-Stonebraker, Samuel; Smith, Sleight; Borowski, Julia; Peters, Ellyn; Gensch, Tobias; Johnson, Heather; Sigman, Matthew; Doyle, Abigail. Linking Mechanistic Analysis of Catalytic Reactivity Cliffs to Ligand Classification. ChemRxiv, May12, 2021. https://doi.org/10.26434/chemrxiv.14388557.v1
Saebi, M.; Nan, B.; Herr, J.; Wahlers, J.; Guo, Z.; Zuranski, A. M.; Kegej, T.; Norrby, P.-O.; Doyle, A. G.; Wiest, O.; Chawla, N., Wiest, O. On the Use of Real-World Data Sets for Reaction Yield Prediction. Chem. Sci., 2023, 14, 4997-5005. https://doi.org/10.1039/D2SC06041H
Jones, K.E.; Park, B.; Doering, N.A.; Baik, M.H.; Sarpong, R. Rearrangements of the Chrysanthenol Core: Application to a Formal Synthesis of Xishacorene B. J. Am. Chem. Soc. 2021, 143, 20482–20490 https://doi.org/10.1021/jacs.1c10804
Zell D; Kingston C; Jermaks J; Smith S.R.; Seeger N; Wassmer J; Sirois, L.E.; Han, C.; Zhang, H.; Sigman, M.S.; Gossling, F., Stereoconvergent and -divergent Synthesis of Tetrasubstituted Alkenes by Nickel-Catalyzed Cross-Couplings. J. Am. Chem. Soc. 2021, 143, 45,19078 -19090. https://doi.org/10.1021/jacs.1c08399
Hardy, M.A.; Nan, B.; Wiest, O.; Sarpong, R. Strategic elements in computer-aided retrosynthesis: A case study of the pupukeanane natural products Tetrahedron 2022, 103, 132584 https://doi.org/10.1016/j.tet.2021.132584
Newman-Stonebraker, S. H.; Smith, S. R.; Borowski, J. E.; Peters, E.; Gensch, T.; Johnson, H. C.; Sigman, M. S.; Doyle, A. G., Univariate classification of phosphine ligation state and reactivity in cross-coupling catalysis. Science 2021, 374, 301-308 science.org/doi/10.1126/science.abj4213
Kariofillis S, Jiang S, Żurański A, Gandhi S, Martinez Alvarado J, Doyle A. Using Data Science to Guide Aryl Bromide Substrate Scope Analysis in a Ni/Photoredox-Catalyzed Cross-Coupling with Acetals as Alcohol-Derived Radical Sources. J. Am. Chem. Soc. 2022, 144 ASAP . https://pubs.acs.org/doi/10.1021/jacs.1c12203