Journal article

Publication year: 2017

Pages: 9097-9099

Journal: Journal of the American Chemical Society

Volume number: 139

Issue number: 27

DOI Link: https://doi.org/10.1021/jacs.7b04593

Publisher: American Chemical Society

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-d(3)-methylcarbene undergoes ring expansion to 1-d(3)-methylcyclobutene. This predicted change in reactivity constitutes the first example of a kinetic isotope effect that discriminates between the formation of two products.

Harvard Citation style: Nandi, A., Gerbig, D., Schreiner, P., Borden, W. and Kozuch, S. (2017) Isotope-Controlled Selectivity by Quantum Tunneling: Hydrogen Migration versus Ring Expansion in Cyclopropylmethylcarbenes, Journal of the American Chemical Society, 139(27), pp. 9097-9099. https://doi.org/10.1021/jacs.7b04593

APA Citation style: Nandi, A., Gerbig, D., Schreiner, P., Borden, W., & Kozuch, S. (2017). Isotope-Controlled Selectivity by Quantum Tunneling: Hydrogen Migration versus Ring Expansion in Cyclopropylmethylcarbenes. Journal of the American Chemical Society. 139(27), 9097-9099. https://doi.org/10.1021/jacs.7b04593