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Experimental evidence for heavy-atom tunneling in the ring-opening of cyclopropylcarbinyl radical from intramolecular 12C/13C kinetic isotope effects.
The intramolecular (13)C kinetic isotope effects for the ring-opening of cyclopropylcarbinyl radical were determined over a broad temperature range. The observed isotope effects are unprecedentedlyExpand
Entropic intermediates and hidden rate-limiting steps in seemingly concerted cycloadditions. Observation, prediction, and origin of an isotope effect on recrossing.
An unusual intramolecular kinetic isotope effect (KIE) in the reaction of dichloroketene with cis-2-butene does not fit with a simple asynchronous cycloaddition transition state, but it can beExpand
Isotope effect, mechanism, and origin of catalysis in the decarboxylation of mandelylthiamin.
The mechanism of decarboxylations in water and the catalysis of mandelylthiamin (MTh) decarboxylation by pyridinium ions is explored. It has been recently proposed that a decarboxylation step formingExpand