Linear Free Energy Relationship Studies of the Dimethyldioxirane C-H Bond Insertion Reaction

Article abstract of DOI:10.1021/jo00122a059

The relative rates of reaction of a series of p-substituted cumenes with dimethyldioxirane have been studied.The products are the corresponding cumyl alcohols.Treatment of the rate data with the Hammett substituent constants reveals that the insertion reaction is an electrophilic process with ρ = -2.76.Similar tretment of the data with the Brown-Okamoto substituent constants gives ρ⁺ = -1.61.The second-order rate constants for the reaction of a series of substituted adamantanes with dimethyldioxirane were also determined.Again, the products are the corresponding adamantanols.The rate constants were correlated with several types of substituent constants.The best correlations were obtained with the Taft ?^* and ?_I constants which gave ρ^* = -1.08 and ρ_I = -2.39, respectively.Thus, the insertion reaction in this aliphatic system is also electrophilic.