Transition Metal Catalysis
We leverage advanced computational tools to study mechanisms of transition metal-catalyzed reactions for C–H/C–C bond activation, alkene functionalization, and cross-coupling reactions. We elucidate the complex roles of ligands and directing groups by accessing non-covalent interactions, strain and flexibility effects.
Research Interests
Our research aims to provide new insights into mechanisms, reactivity, and selectivity in a broad range of transition metal-catalyzed reactions.
Catalytic Reaction Mechanisms
We leverage advanced computational tools to study mechanisms of a variety of transition metal-catalyzed reactions, such as C–H/C–C bond activation, alkene functionalization, cross-coupling, polymerization, and glycosylation reactions. These studies revealed previously unrecognized mechanisms, factors that determine pathway selectivities, and unique reactivity and selectivity control.
Representative Publications:
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"Cut-and-sew" functionalization of strained C–C bonds
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JACS 2015, 137, 8274–8283. DOI: 10.1021/jacs.5b04691
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Substrate-dependent mechanisms in Ni-catalyzed C−H functionalization
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JACS 2017, 139, 9909–9920. DOI: 10.1021/jacs.7b03548
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Aromatization-promoted C−C bond activation
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Nature 2019, 567, 373–378. DOI: 10.1038/s41586-019-0926-8
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Ni-catalyzed vicinal diborylation of aryl halides
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Nature, 2025, 644, 102–108. DOI: 10.1038/s41586-025-09284-5
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Catalyst–Substrate Interactions
Detailed understanding of ligand effects is of pivotal importance for the development of effective catalysts for regio- and stereoselective transformations. Our studies reveal new types of ligand effects that can be leveraged in rational catalyst design. These include several types of underappreciated non-covalent interactions, such as C–H/C–H, C–H/C–F, and lone pair/π interactions. With quantitative transition state analysis tools, such as energy decomposition analysis (EDA), our research provides a more precise understanding of the nature of ligand effects and the dominant type of catalyst-substrate interactions that can be further leveraged to enhance catalyst performance.
Representative Publications:
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Ligand–substrate dispersion in Cu hydride catalysis:
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JACS 2017, 139, 16548–16555. DOI: 10.1021/jacs.7b07373
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Leveraging ligand–substrate dispersion in catalyst design
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JACS 2018, 140, 13976–13984. DOI: 10.1021/jacs.8b09565
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Catalyst and nucleophile effects on regioselectivity in nucleopallation
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JACS 2019, 141, 11892–11904. DOI: 10.1021/jacs.9b02893
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Enantioselective halogen atom transfer
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Nature 2025, 640, 107–113. DOI: 10.1038/s41586-025-08784-8
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Directing Group Effects
Directing groups (DGs) are a commonly used strategy to control reactivity and selectivity of C–H, C–C, and alkene functionalizations. Our research investigates how steric and electronic properties of the directing groups, as well as their flexibility, affect their performance in transition metal catalysis.
Representative Publications:
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Directing group and tether length effects on transition state ring strain in Ag-catalyzed C-H amination
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JACS 2022, 144, 2735–2746. DOI: 10.1021/jacs.1c12111
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Transient directing group rigidity promotes enantioselective hydrofunctionalization of alkenes
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Angew. Chem. Int. Ed. 2023, 135, e202304013. DOI: 10.1002/anie.202304013
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Chiral transient directing group enables atoposelective β-H elimination
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JACS 2025, 147, 40244–40252. DOI: 10.1021/jacs.5c10118
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Ligand Flexibility and Hemilability
Unlike ligand steric or electronic properties, the flexibility effects of ancillary ligands in transition metal catalysis are much less understood. Our research investigates the unique roles of conformationally flexible and hemilabile ligands in promoting reactivity and controlling selectivity.
Representative Publications:
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Ligand flexibility promotes both reactivity and selectivity in Rh-catalyzed hydroboration
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JACS 2021, 143, 4801–4808. DOI: 10.1021/jacs.1c01303
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Hemilabile bioxazoline ligand enables enantioselective migratory insertion in Ni-catalyzed 1,2-dicarbofunctionalization of alkenes
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JACS 2022, 144, 19337–19343. DOI: 10.1021/jacs.2c06636
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Quinones as a family of hemilabile and redox-active ligands in Ni catalysis
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Angew. Chem. Int. Ed. 2024, 63, e202411870. DOI: 10.1002/anie.202411870
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Shape and flexibility of chiral dirhodium tetracarboxylate catalysts in solution affect the enantioinduction model for alkene cyclopropanation
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JACS 2025, 147, 14694–14704. DOI: 10.1021/jacs.5c03007
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Publications by Research Areas
Our research covers a broad range of transition metal catalysts and different types of bond formation reactions.