Reaction of 1,2-dioxetanes with heteroatom nucleophiles: Adduct formation by nucleophilic attack at the peroxide bond

Article abstract of DOI:10.1021/ja00040a017

The reactions of 3,3-disubstituted 1,2-dioxetanes 1 with numerous heteroatom nucleophiles, e.g., R₂NH, R₃N, RSH, R₂S, CN^-, SCN^-, Br^-, Cl^-, OH^-, and O₂^*-, were investigated. Initial nucleophilic substitution at the sterically less hindered site of the dioxetane peroxide bond leads to addition, deoxygenation, and fragmentation products. The observed S_N2 chemistry was substantiated with the dioxetane le because bromide ion displacement by the proximate alkoxide ion site afforded epoxide products. Thus, with anionic nucleophiles the epoxy alcohol 8c was obtained in appreciable amounts, and triethylamine and DABCO gave with 1c exclusively the alkoxyammonium epoxides 4c and 5c. Moreover, the labile alkoxysulfonium epoxide 6c was detected as an intermediate in the deoxygenation of 1c by diphenyl sulfide. From the reaction of 1b-d with secondary amines were isolated the hydroxylamine derivatives 2 and 3, and the cyanide and thiocyanate ions gave with 1c,d five-membered-ring insertion products, namely, the carbonates 9c,d and the cyclic sulfite 10c.