The Chemistry of Methyl Hypofluorite: Its Reactions with Various Unsaturated Centers

Article abstract of DOI:10.1021/jo00094a047

Methyl hypofluorite was until recently grouped as a hypothetical member of those smallest organic molecules which had not been synthesized.Passing F2 through a solution of methanol in MeCN or PrCN resulted in this successful preparation.MeOF is an unique reagent, since it generates the novel electrophilic methoxylium moiety in contrast to the much more common methoxide group.This hypofluorite was reacted with several types of olefins including benzylic, cyclic, bicyclic, straight chain, and steroidal ones.In most cases the regioselectivity is very good, reflecting the unique polarization of the reagent: MeO^δ(+)F^δ(-).The stereoselectivity tends to be less emphasized, but usually anti addition is dominant.