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Isotope-Controlled Selectivity by Quantum Tunneling: Hydrogen Migration versus Ring Expansion in Cyclopropylmethylcarbenes

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    Isotope-Controlled Selectivity by Quantum Tunneling: Hydrogen Migration versus Ring Expansion in Cyclopropylmethylcarbenes
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    † Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva 841051, Israel
    ‡ Justus-Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany
    § Center for Advanced Scientific Computing and Modeling (CASCAM), Department of Chemistry, University of North Texas, Denton, Texas 76203, United States
    *[email protected]
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2017, 139, 27, 9097–9099
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    https://doi.org/10.1021/jacs.7b04593
    Published June 21, 2017
    Copyright © 2017 American Chemical Society
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    Abstract

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    Using the tunneling-controlled reactivity of cyclopropylmethylcarbene, we demonstrate the viability of isotope-controlled selectivity (ICS), a novel control element of chemical reactivity where a molecular system with two conceivable products of tunneling exclusively produces one or the other, depending only on isotopic composition. Our multidimensional small-curvature tunneling (SCT) computations indicate that, under cryogenic conditions, 1-methoxycyclopropylmethylcarbene shows rapid H-migration to 1-methoxy-1-vinylcyclopropane, whereas deuterium-substituted 1-methoxycyclopropyl-d3-methylcarbene undergoes ring expansion to 1-d3-methylcyclobutene. This predicted change in reactivity constitutes the first example of a kinetic isotope effect that discriminates between the formation of two products.

    Copyright © 2017 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.7b04593.

    • Benchmark analysis, description of systems with more than one substituent, explanation of substituent effects, XYZ geometries, complete kinetic tables as a function of temperature, example of POLYRATE output, and full refs 15 and 16 (PDF)

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    This article is cited by 26 publications.

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    22. Cláudio M. Nunes, Luís P. Viegas, Samuel A. Wood, José P. L. Roque, Robert J. McMahon, Rui Fausto. Heavy‐Atom Tunneling Through Crossing Potential Energy Surfaces: Cyclization of a Triplet 2‐Formylarylnitrene to a Singlet 2,1‐Benzisoxazole. Angewandte Chemie International Edition 2020, 59 (40) , 17622-17627. https://doi.org/10.1002/anie.202006640
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2017, 139, 27, 9097–9099
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.7b04593
    Published June 21, 2017
    Copyright © 2017 American Chemical Society
    Request reuse permissions

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