Electric field-catalyzed single-molecule Diels-Alder reaction dynamics

Chen Yang; Zitong Liu; Yanwei Li; Shuyao Zhou; Chenxi Lu; Yilin Guo; Melissa Ramirez; Qingzhu Zhang; Yu Li; Zhirong Liu; K N Houk; Deqing Zhang; Xuefeng Guo

doi:10.1126/sciadv.abf0689

Electric field-catalyzed single-molecule Diels-Alder reaction dynamics

Sci Adv. 2021 Jan 20;7(4):eabf0689. doi: 10.1126/sciadv.abf0689. Print 2021 Jan.

Authors

Chen Yang¹, Zitong Liu², Yanwei Li^{3

4}, Shuyao Zhou¹, Chenxi Lu³, Yilin Guo¹, Melissa Ramirez³, Qingzhu Zhang⁴, Yu Li¹, Zhirong Liu¹, K N Houk⁵, Deqing Zhang⁶, Xuefeng Guo⁷

Affiliations

¹ Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China.
² Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
³ Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095, USA.
⁴ Environment Research Institute, Shandong University, Qingdao 266237, P. R. China.
⁵ Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095, USA. guoxf@pku.edu.cn dqzhang@iccas.ac.cn houk@chem.ucla.edu.
⁶ Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China. guoxf@pku.edu.cn dqzhang@iccas.ac.cn houk@chem.ucla.edu.
⁷ Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China. guoxf@pku.edu.cn dqzhang@iccas.ac.cn houk@chem.ucla.edu.

Abstract

Precise time trajectories and detailed reaction pathways of the Diels-Alder reaction were directly observed using accurate single-molecule detection on an in situ label-free single-molecule electrical detection platform. This study demonstrates the well-accepted concerted mechanism and clarifies the role of charge transfer complexes with endo or exo configurations on the reaction path. An unprecedented stepwise pathway was verified at high temperatures in a high-voltage electric field. Experiments and theoretical results revealed an electric field-catalyzed mechanism that shows the presence of a zwitterionic intermediate with one bond formation and variation of concerted and stepwise reactions by the strength of the electric field, thus establishing a previously unidentified approach for mechanistic control by electric field catalysis.

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