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

Michal Juríček; Nathan L. Strutt; Jonathan C. Barnes; Anna M. Butterfield; Edward J. Dale; Kim K. Baldridge; J. Fraser Stoddart; Jay S. Siegel

doi:10.1038/nchem.1842

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

Michal Juríček, Nathan L. Strutt, Jonathan C. Barnes, Anna M. Butterfield, Edward J. Dale, Kim K. Baldridge, J. Fraser Stoddart, Jay S. Siegel

Chemistry

Research output: Contribution to journal › Article › peer-review

120 Scopus citations

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.

Original language	English (US)
Pages (from-to)	222-228
Number of pages	7
Journal	Nature chemistry
Volume	6
Issue number	3
DOIs	https://doi.org/10.1038/nchem.1842
State	Published - Mar 2014

ASJC Scopus subject areas

Chemistry(all)
Chemical Engineering(all)

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10.1038/nchem.1842

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@article{69968caf7c164396acfd1a9f4dc87d56,

title = "Induced-fit catalysis of corannulene bowl-to-bowl inversion",

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.",

author = "Michal Jur{\'i}{\v c}ek and Strutt, {Nathan L.} and Barnes, {Jonathan C.} and Butterfield, {Anna M.} and Dale, {Edward J.} and Baldridge, {Kim K.} and Stoddart, {J. Fraser} and Siegel, {Jay S.}",

note = "Funding Information: 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).",

year = "2014",

month = mar,

doi = "10.1038/nchem.1842",

language = "English (US)",

volume = "6",

pages = "222--228",

journal = "Nature Chemistry",

issn = "1755-4330",

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number = "3",

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T1 - Induced-fit catalysis of corannulene bowl-to-bowl inversion

AU - Juríček, Michal

AU - Strutt, Nathan L.

AU - Barnes, Jonathan C.

AU - Butterfield, Anna M.

AU - Dale, Edward J.

AU - Baldridge, Kim K.

AU - Stoddart, J. Fraser

AU - Siegel, Jay S.

N1 - Funding Information: 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).

PY - 2014/3

Y1 - 2014/3

N2 - 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.

AB - 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.

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DO - 10.1038/nchem.1842

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JO - Nature Chemistry

JF - Nature Chemistry

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ER -

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

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CCDC 950390: Experimental Crystal Structure Determination

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

Abstract

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CCDC 950390: Experimental Crystal Structure Determination

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