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

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, depen...

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Published inJournal of the American Chemical Society Vol. 139; no. 27; pp. 9097 - 9099
Main Authors Nandi, Ashim, Gerbig, Dennis, Schreiner, Peter R, Borden, Weston Thatcher, Kozuch, Sebastian
Format Journal Article
LanguageEnglish
Published United States 12.07.2017
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Summary: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-d -methylcarbene undergoes ring expansion to 1-d -methylcyclobutene. This predicted change in reactivity constitutes the first example of a kinetic isotope effect that discriminates between the formation of two products.
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ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.7b04593