Polar effects in free-radical reactions. The paradox of reduction of alkyl iodides and reductive alkylation of alkenes by strong oxidants (t-BuOOH, Pb.(OAc)4)

A study reports on new synthetic developments which, beginning from the paradoxical reduction of alkyl iodides by the oxidant t-BuOOH, have resulted in the reductive alkylation of simple alkenes by electrophilic carbon-centered radicals. A new methodology for the reductive alkylation of electron-poor alkenes by nucleophilic radicals generated by Pb(IV) oxidation of carboxylic acids is also described. These new synthetic techniques were made possible by analysis of the polar effects involved and by knowing the absolute rate constants of some key basic steps of the reactions.