Reactivity and Selectivity Rules in Organic and Organometallic Reactions
We are developing computational models to quantitatively describe the origins of reactivity and selectivity in organocatalytic and transition metal-catalyzed reactions. We perform quantum mechanical calculations to explore the reaction mechanism, followed by thorough analysis on various stereoelectronic effects to predict how changes of the catalyst structure, substituents, and solvent affect rate and selectivity. We use quantitative energy decomposition methods to dissect the key interactions in the transition state and provide chemically meaningful interpretation to the computed reactivity and selectivity. We apply these computational studies to a broad range of organic and organometallic reactions, such as C–H and C–C bond activations, coupling reactions, olefin metathesis, and polymerization reactions.
Catalyst Screening and Prediction
We are developing a multi-scale computational screening protocol which could efficiently rank the catalysts based on ligand-substrate interaction energies in the transition state.
Applications of Computational Chemistry in Understanding Organic Chemistry
We are collaborating with experimental groups at Pitt and many other institutions to solve problems in organic chemistry using computational methods and programs. Our goal is to establish the most effective strategy to use modern computational methods and hardware to help address the grand challenges in synthetic chemistry.
- "Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions," Gavin O. Jones, Peng Liu, K. N. Houk and Stephen L. Buchwald, J. Am. Chem. Soc. 132, 6205 (2010)
- "Suzuki−Miyaura Cross-Coupling of Aryl Carbamates and Sulfamates: Experimental and Computational Studies," Kyle W. Quasdorf, Aurora Antoft-Finch, Peng Liu, Amanda L. Silberstein, Anna Komaromi, Tom Blackburn, Stephen D. Ramgren, K. N. Houk, Victor Snieckus, and Neil K. Garg, J. Am. Chem. Soc. 133, 6352 (2011)
- "Conversion of amides to esters by the nickel-catalysed activation of amide C–N bonds," Liana Hie, Noah F. Fine Nathel, Tejas K. Shah, Emma L. Baker, Xin Hong, Yun-Fang Yang, Peng Liu, K. N. Houk& Neil K. Garg, Nature, 524, 79 (2015)
- "Palladium-Catalyzed Meta-Selective C–H Bond Activation with a Nitrile-Containing Template: Computational Study on Mechanism and Origins of Selectivity," Yun-Fang Yang, Gui-Juan Cheng, Peng Liu, Dasheng Leow, Tian-Yu Sun, Ping Chen, Xinhao Zhang, Jin-Quan Yu, Yun-Dong Wu, and K. N. Houk, J. Am. Chem. Soc. 136, 344 (2014)
- "Z-Selectivity in Olefin Metathesis with Chelated Ru Catalysts: Computational Studies of Mechanism and Selectivity," Peng Liu, Xiufang Xu, Xiaofei Dong, Benjamin K. Keitz, Myles B. Herbert, Robert H. Grubbs, and K. N. Houk, J. Am. Chem. Soc. 134, 1464 (2012)
- "Methylene Blue-Catalyzed Oxidative Cleavage of N-Carbonylated Indoles," Kui Wu, Cheng Fang, Sarbjeet Kaur, Peng Liu, Ting Wang, Synthesis 2018, 50, A–K.
- "Traversing Steric Limitations via Cooperative Lewis Base/Pd Catalysis: An Enantioselective Synthesis of α‐Branched Esters using 2‐Substituted Electrophiles", Kevin Schwarz, Colin Pearson, Gabriel Cintron-Rosado, Peng Liu,Thomas Neil Snaddon, Angewandte Chemie International Edition (2018).
"C(alkenyl)−H Activation via Six-Membered Palladacycles: Catalytic 1,3-Diene Synthesis," Mingyu Liu, Pusu Yang, Malkanthi K. Karunananda, Yanyan Wang, Peng Liu, and Keary M. Engle, J. Am. Chem. Soc. (2018).
"An Initiation Kinetics Prediction Model Enables Rational Design of Ruthenium Olefin Metathesis Catalysts Bearing Modified Chelating Benzylidenes" Shao-Xiong Luo, Keary M. Engle, Xiaofei Dong, Andrew Hejl, Michael K. Takase, Lawrence M. Henling, Peng Liu, K. N. Houk, and Robert H. Grubbs, ACS Catalysis (2018).
"Disentangling Ligand Effects on Metathesis Catalyst Activity: Experimental and Computational Studies of Ruthenium–Aminophosphine Complexes Crystal," K. Chu, Tzu-Pin Lin, Huiling Shao, Allegra L. Liberman-Martin, Peng Liu, and Robert H. Grubbs, Journal of the American Chemical Society (2018).