ORGN 118 |
| Alkene radical cation 2+• was generated under non-oxidizing conditions by heterolytic cleavage of beta-methanesulfonyloxy radical 1•, which was generated by photolysis of PTOC precursor 1. The kinetics of the heterolysis of 1• to give a contact ion pair, the kinetics of collapse of the ion pair, and the kinetics of separation were investigated by competition kinetic methods in several organic solvents. Changes in solvent had minor effects on the heterolysis (khet) and separation rates (ksep) but induced large changes in the rate of ion pair collapse (kcol). Competition and LFP studies showed that the cyclization of 2+• was highly reversible with values of kcycle and kopen greater than 1010 s-1. LFP studies showed that 1• underwent rate limiting protonation (general acid catalysis) in PhCF3 to give cyclized products.
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Process R&D, Physical Organic Chemistry, Heterocycles, Aromatics, Metal-Mediated Reactions
8:00 PM-10:00 PM, Sunday, March 25, 2007 Hyatt Regency Chicago -- Riverside Center, Poster
Division of Organic Chemistry |
