title: Relative rates and approximate rate constants for inter- and intramolecular hydrogen transfer reactions of polymer-bound radicals.
abstract: Measurements of relative rates and rate constants for inter- and intramolecular hydrogen transfer reactions of polymer-bound radicals are reported. The relative rate of reaction of resin-bound primary alkyl radical with tributyltin hydride is about 2 times slower than that of the benchmark reaction in solution. The data do not reveal whether this is due to a reduced rate constant or a lower concentration of tin hydride in the resin phase. Yet the difference between solid and solution reactions is small enough to be neglected, and it appears that rate constants measured in solution can be applied directly to resin-bound radicals. A resin-bound aryl radical abstracts a hydrogen atom rapidly (k = 3 x 10(6) s(-1)) from its own polymer backbone and linker, and a simplified view of the resin as a "solvent" is suggested for predicting such effects with other polymers and linkers. Rapid cyclizations of resin-bound aryl radicals will be possible, but slower cyclizations and most bimolecular reactions will be difficult due to the competing polymer/linker hydrogen transfer.
authors.affiliation: Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA. curran@pitt.edu
authors.forename: Dennis P
authors.initials: DP
authors.lastname: Curran
authors.forename: Fanglong
authors.initials: F
authors.lastname: Yang
authors.forename: Jae-Ho
authors.initials: JH
authors.lastname: Cheong