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Kinetic Studies of a Fast, Reversible Alkene Radical Cation Cyclization Reaction
journal contribution
posted on 2007-03-02, 00:00 authored by John H. Horner, Martin NewcombThe radical cation formed by mesylate heterolysis from the 1,1-dimethyl-7,7-diphenyl-2-mesyloxy-6-heptenyl radical was studied in several solvents. Computational results suggest that the initially formed
acyclic radical cation is a resonance hybrid with partial positive charge in both double bonds of 1,1-diphenyl-7-methyl-1,6-octadiene (10). Thiophenol trapping was used as the competing reaction for kinetic
determinations. The acyclic radical cation rapidly equilibrates with a cyclic distonic radical cation, and
thiophenol trapping gives acyclic product 10 and cyclic products, mainly trans-1-(diphenylmethyl)-2-(1-methylethenyl)cyclopentane (11). The rate constants for cyclization at ambient temperature were k =
(0.5−2) × 1010 s-1, and those for ring opening were k = (1.5−9) × 1010 s-1. Laser flash photolysis
studies in several solvents show relatively slow processes (k = (2.5−260) × 105 s-1) that involve rate-limiting trapping reactions for the equilibrating radical cations. In mixtures of fluoroalcohols RfCH2OH
in trifluoromethylbenzene, variable-temperature studies display small, and in one case a negative, activation
energies, requiring equilibration reactions prior to the rate-limiting processes. Fast equilibration of acyclic
and cyclic radical cations implies that product ratios can be controlled by the populations of the acyclic
and cyclic species and relative rate constants for trapping each.