Electron-Transfer-Induced Reductive Cleavage of Phthalans:  Reactivity and Synthetic Applications

The behavior of phthalan ( 1a ) was investigated under conditions of electron transfer from alkali metals in aprotic solvents. Reaction with lithium in the presence of a catalytic amount of naphthalene in THF led to the reductive cleavage of an arylmethyl carbon−oxygen bond, with formation of a stable dilithium compound. Trapping of this intermediate with several electrophiles (alkyl halides, carbonyl derivatives, CO 2 ) was successful. The extension of this procedure to several substituted phthalans ( 1b − i ) was investigated, and the regiochemistry as well as the synthetic usefulness of these reactions are discussed.