Transition-state geometry measurements from (13)c isotope effects. The experimental transition state for the epoxidation of alkenes with oxaziridines.

Journal of the American Chemical Society
Jennifer S HirschiDaniel A Singleton

Abstract

We here suggest and evaluate a methodology for the measurement of specific interatomic distances from a combination of theoretical calculations and experimentally measured (13)C kinetic isotope effects. This process takes advantage of a broad diversity of transition structures available for the epoxidation of 2-methyl-2-butene with oxaziridines. From the isotope effects calculated for these transition structures, a theory-independent relationship between the C-O bond distances of the newly forming bonds and the isotope effects is established. Within the precision of the measurement, this relationship in combination with the experimental isotope effects provides a highly accurate picture of the C-O bonds forming at the transition state. The diversity of transition structures also allows an evaluation of the Schramm process for defining transition-state geometries on the basis of calculations at nonstationary points, and the methodology is found to be reasonably accurate.

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Citations

Jan 1, 1987·Immunology Today·P Braquet, M Rola-Pleszcynski
Sep 22, 2011·Biochemistry·Rafael G Silva, Vern L Schramm
Apr 18, 2012·Organic Letters·Mathew J Vetticatt, Daniel A Singleton
Jan 21, 2016·Journal of the American Chemical Society·Chiara CollettoIgor Larrosa
May 18, 2016·Journal of the American Chemical Society·Myles B PoulinVern L Schramm
Aug 20, 2016·Journal of the American Chemical Society·Daniel Roston, Qiang Cui
Dec 23, 2016·Journal of the American Chemical Society·Eugene E KwanEric N Jacobsen
Feb 24, 2017·Journal of the American Chemical Society·Thomas H WestAndrew D Smith
Mar 2, 2017·The Journal of Physical Chemistry. a·Szymon ŻaczekAgnieszka Dybala-Defratyka
Apr 6, 2017·Journal of the American Chemical Society·Hannah R Aziz, Daniel A Singleton
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