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Induced-fit catalysis of corannulene bowl-to-bowl inversion

Nature Chemistry volume 6, pages 222228 (2014) | Download Citation

Abstract

Stereoelectronic complementarity between the active site of an enzyme and the transition state of a reaction is one of the tenets of enzyme catalysis. This report illustrates the principles of enzyme catalysis (first proposed by Pauling and Jencks) through a well-defined model system that has been fully characterized crystallographically, computationally and kinetically. Catalysis of the bowl-to-bowl inversion processes that pertain to corannulene is achieved by combining ground-state destabilization and transition-state stabilization within the cavity of an extended tetracationic cyclophane. This synthetic receptor fulfils a role reminiscent of a catalytic antibody by stabilizing the planar transition state for the bowl-to-bowl inversion of (ethyl)corannulene (which accelerates this process by a factor of ten at room temperature) by an induced-fit mechanism first formulated by Koshland.

  • Compound C48H40N4 4+

    Tetracationic tetrapyriduna-tetrabenzyna-cyclododecaphane

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Acknowledgements

The authors thank M. Stuparu for synthesizing bromocorannulene and C. L. Stern for performing the X-ray crystallographic analysis. This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdul-Aziz City for Science and Technology (KACST) and Northwestern University (NU) (Project 34-947). The authors would like to thank both KACST and NU for their continued support of this research. We also acknowledge support from the World Class University Program (R-31-2008-000-10055-0) in Korea. M.J. gratefully acknowledges The Netherlands Organisation for Scientific Research and the Marie Curie Cofund Action (Rubicon Fellowship). N.L.S. and E.J.D. are supported by a Graduate Research Fellowship from the National Science Foundation. J.C.B. is supported by a National Defense Science and Engineering Graduate Fellowship from the Department of Defense and gratefully acknowledges receipt of a Ryan Fellowship from the NU International Institute for Nanotechnology. K.K.B. and J.S.S. gratefully acknowledge the Swiss National Science Foundation, the Qian Ren Scholar Program of China and the Synergetic Innovation Center of Chemical Science and Engineering (Tianjin).

Author information

Affiliations

  1. Center for the Chemistry of Integrated Systems, Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA

    • Michal Juríček
    • , Nathan L. Strutt
    • , Jonathan C. Barnes
    • , Edward J. Dale
    •  & J. Fraser Stoddart
  2. Organic Chemistry Institute (OCI), University of Zürich, Winterthurerstrasse 190, Zürich, CH-8057, Switzerland

    • Anna M. Butterfield
    • , Kim K. Baldridge
    •  & Jay S. Siegel
  3. School of Pharmaceutical Science and Technology, Tianjin University (A210/Building 24), 92 Weijin Road, Nankai District, Tianjin, 300072 PRC, China

    • Kim K. Baldridge
    •  & Jay S. Siegel

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Contributions

M.J., N.L.S., J.C.B., J.F.S. and J.S.S. conceived the project and prepared the manuscript. M.J., J.C.B., A.M.B. and E.J.D. synthesized the different molecules studied in this work. M.J. and N.L.S. carried out NMR studies. K.K.B. performed DFT calculations. M.J., N.L.S., J.C.B., K.K.B., J.F.S. and J.S.S. investigated the bowl-to-bowl inversion process.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Jay S. Siegel.

Supplementary information

PDF files

  1. 1.

    Supplementary information

    Supplementary information

Crystallographic information files

  1. 1.

    Supplementary information

    Crystallographic data for compound corannulene  ExBox•4PF6(MeCN)7

Protein data bank files

  1. 1.

    Supplementary information

    Supplementary pdb file for the optimized geometry (B97D/Def2-TZVPP) of the ground state of corannulene-ExBox4+ complex in the gas phase.

  2. 2.

    Supplementary information

    Supplementary pdb file for the optimized geometry (B97D/Def2-TZVPP) of the ground state of corannulene-ExBox4+ complex in Me2CO.

  3. 3.

    Supplementary information

    Supplementary pdb file for the optimized geometry (B97D/Def2-TZVPP) of the transition state of corannulene-ExBox4+ complex in the gas phase.

  4. 4.

    Supplementary information

    Supplementary pdb file for the optimized geometry (B97D/Def2-TZVPP) of the transition state of corannulene-ExBox4+ complex in Me2CO

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DOI

https://doi.org/10.1038/nchem.1842

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