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

Ashim Nandi, Dennis Gerbig, Peter R. Schreiner, Weston Thatcher Borden, Sebastian Kozuch

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

Abstract

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.

Original languageEnglish
Pages (from-to)9097-9099
Number of pages3
JournalJournal of the American Chemical Society
Volume139
Issue number27
DOIs
StatePublished - 12 Jul 2017

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