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)
- "Catalytic, Enantioselective α-Alkylation of Azlactones with Non-Conjugated Alkenes via Directed Nucleopalladation." Nimmagadda, Sri, Mingyu Liu, Malkanthi Karunananda, D. Gao, Omar Apolinar, Jason Chen, Peng Liu, and Keary Engle. (2018).
- "Mechanistically Guided Design of Ligands That Significantly Improve the Efficiency of CuH-Catalyzed Hydroamination Reactions." Thomas, Andy A., Klaus Speck, Ilia Kevlishvili, Zhaohong Lu, Peng Liu, and Stephen L. Buchwald. Journal of the American Chemical Society 140, no. 42 (2018): 13976-13984.
- "Redox‐Active Reagents for Photocatalytic Generation of the OCF3 Radical and (Hetero) Aryl C− H Trifluoromethoxylation." Zheng, Weijia, Johnny W. Lee, Cristian A. Morales‐Rivera, Peng Liu, and Ming‐Yu Ngai. Angewandte Chemie International Edition 57, no. 42 (2018): 13795-13799.
- "H-bonded reusable template assisted paraselective ketonisation using soft electrophilic vinyl ethers," Arun Maji, Amit Dahiya, Gang Lu, Trisha Bhattacharya, Massimo Brochetta, Giuseppe Zanoni, Peng Liu & Debabrata Maiti, NATURE COMMUNICATIONS 9, 3582 (2018).
- "Epimerization of Tertiary Carbon Centers via Reversible Radical Cleavage of Unactivated C(sp3 )−H Bonds," Yaxin Wang, Xiafei Hu, Cristian A. Morales-Rivera,§Guo-Xing Li, Xin Huang, Gang He, Peng Liu and Gong Chen, J. Am. Chem. Soc. (2018)