Reaction of α-peroxy lactones with C,N,P, and s nucleophiles: adduct formation and nucleophile oxidation by nucleophilic attack at and biphilic insertion into the peroxide bond

摘要

The reactions of the α-peroxy lactone 1 with a variety of carbon, nitrogen, phosphorus, and sulfur nucleophiles yield, ion S_N2 attack at the more electrophilic alkoxy oxygen of the peroxide bond, diverse addition and oxygen transfer products, together with the catalytic Grob-type fragmentation. The nature of the nucleophile determines the fate of the open-chain intermediate I. Thus, protic Nucleophiles such as primary and secondary amines and thiols lead to the second intermediate I' Through proton shift subsequent to the S_N2 step, while nonprotic amines and sulfides, as well as Diazoalkanes, lead to oxidation products or to the cycloadducts 10-15.