Tomislav Rovis
Research Interest
Summary
Our group is broadly interested in aspects of catalysis and applying it to problems in synthetic chemistry and chemical biology. We have long been interested in using piano stool Rh(III) complexes for C-H activation under mild conditions and have applied these methods to the synthesis of a wide variety of nitrogen heterocycles of interest to the pharmaceutical industry. These efforts have also brought us to the use and development of artificial metalloenzymes which couple transition metal based reactivity with a genetically encoded ligand environment. In parallel, we have been interested in using light to drive catalysis, with increasing emphasis on the use of low energy deep red or near infrared light, whose tolerance to reactive functional groups or catalytically generated intermediates leads to more benign, higher yielding transformations. Another consequence of low energy light is its deeper tissue penetration which we have harnessed to address problems in proximity labelling for chemical biology applications.
“Spin-Forbidden Excitation Enables Infrared Photoredox Catalysis.” B. D. Ravetz, N. E. S. Tay, C. L. Joe*, M. Sezen-Edmonds, M. A. Schmidt, Y. Tan, J. M. Janey, M. D. Eastgate, T. Rovis*. ACS Cent. Sci. 2020, 6, 2053-2059.
“Diastereoselective Three-Component 3,4-Amino Oxygenation of 1,3-Dienes Catalyzed by a Cationic Heptamethylindenyl Rhodium(III) Complex.” F. Burg, T. Rovis*. J. Am. Chem. Soc. 2021, 143, 17964-17969.
“Tuning through-space interactions via the secondary coordination sphere of an artificial metalloenzyme leads to enhanced Rh(III)-catalysis.” I. S. Hassan, J. T. Fuller, V. N. Dippon, A. N. Ta, M. W. Danneman, B. R. McNaughton,* A. N. Alexandrova,* T. Rovis.* Chem. Sci. 2022, 13, 9220–9224.
“Targeted Activation in Localized Protein Environments via Deep Red Photoredox Catalysis.” N. E. S. Tay, K. A. Ryu, J. L. Weber, A. K. Olow, D. C. Cabanero, D. R. Reichman, R. C. Oslund, O. O. Fadeyi, T. Rovis.* Nature Chem. 2023, 15, 101-109.
“Photocatalytic Activation of Aryl(trifluoromethyl) Diazos to Carbenes for High-Resolution Protein Labeling with Red Light.” D. C. Cabanero, S. K. Kariofillis, A. C. Johns, J. Kim, J. Ni, S. Park, D. L. Parker Jr., C. P. Ramil, X. Roy, N. H. Shah*, T. Rovis* J. Am. Chem. Soc. 2024, 146, 1337-1345.
“Crafting Unnatural Peptide Macrocycles via Rh(III)-Catalyzed Carboamidation” C. W. Lamartina, C. A. Chartier, J. M. Hirano, N. H. Shah*, T. Rovis*. J. Am. Chem. Soc. 2024, 146, 20868-20877.
“Low-Energy Photoredox Catalysis.” D. C. Cabanero, T. Rovis. Nat. Rev. Chem. 2025, 9, 28-45.