title: Quantitating the effect of an ortho substituent on cyclization and intramolecular hydrogen-transfer reactions of aryl radicals.
abstract: Reduction of allyl 2-iodobenzyl malonates with triphenyltin hydrides generates aryl radicals that partition between 6-exo cyclization, 7-endo cyclization, and 1,5-hydrogen atom transfer. Rate constants for all of these processes are high (>10(8) M(-)(1) s(-)(1)), and the rates are only marginally reduced (<33%) by the introduction of methyl group ortho to the reacting radical.
authors.affiliation: Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA. curran@pitt.edu
authors.forename: Dennis P
authors.initials: DP
authors.lastname: Curran
authors.forename: Neil
authors.initials: N
authors.lastname: Fairweather
mesh_terms: D000478:Alkylation; D002384:Catalysis; D003500:Cyclization; D006844:Hydrocarbons, Cyclic / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007202:Indicators and Reagents; D007700:Kinetics; D008314:Malonates / Q000737:chemistry*; D008745:Methylation; D015394:Molecular Structure
chemical_list: D006844:Hydrocarbons, Cyclic; D007202:Indicators and Reagents; D008314:Malonates; D006859:Hydrogen