Cyclopropylcarbinyl → Homoallyl-Type Ring Opening of Ketyl Radical Anions. Structure/Reactivity Relationships and the Contribution of Solvent/Counterion Reorganization to the Intrinsic Barrier
Following a protocol developed by Mathivanan, Johnston, and Wayner (J. Phys. Chem. 1995, 99, 8190−8195), the radical anions of several cyclopropyl- and oxiranyl-containing carbonyl compounds were generated in an effort to measure the rate constants for their ring opening (ko) by laser flash photolysis. The results of these experiments are compared to those obtained from earlier electrochemical studies, and the combined data set is used to rationalize the kinetics of radical anion ring opening in a general context by using Savéant's theory pertaining to stepwise dissociative electron transfer (Acc. Chem. Res. 1993, 26, 455−461). Compared to cyclopropylcarbinyl → homoallyl rearrangements of neutral free radicals, at comparable driving force, the radical anion ring openings are slightly slower. The small difference in rate is attributed to the contribution of an additional, approximately 2 kcal/mol, solvent reorganization component for the radical anion rearrangements. The solvent reorganization energy for ring opening of these radical anions is believed to be small because the negative charge does not move appreciably in the progression reactant → transition state → product.
Repository citation: Tanko, J. M.; Gillmore, Jason G.; Friedline, Robert; and Chahma, M'hamed, "Cyclopropylcarbinyl → Homoallyl-Type Ring Opening of Ketyl Radical Anions. Structure/Reactivity Relationships and the Contribution of Solvent/Counterion Reorganization to the Intrinsic Barrier" (2005). Faculty Publications. Paper 1042.
Published in: Journal of Organic Chemistry, Volume 70, Issue 10, May 13, 2005, pages 4170-4173. Copyright © 2005 American Chemical Society, Washington, D.C..