THE CHEMISTRY OF METHYL HYPOFLUORITE - ITS REACTIONS WITH VARIOUS UNSATURATED CENTERS

Methyl hypofluorite was until recently grouped as a hypothetical membe r of those smallest organic molecules which had not been synthesized. Passing F-2 through a solution of methanol in MeCN or PrCN resulted in its successful preparation. MeOF is an unique reagent, since it gener ates the novel electrophilic methoxylium moiety in contrast to the muc h more common methoxide group. This hypofluorite was reacted with seve ral types of olefins including benzylic, cyclic, bicyclic, straight ch ain, and steroidal ones. In most cases the regioselectivity is very go od, reflecting the unique polarization of the reagent: MeO(delta+)F(de lta-). The stereoselectivity tends to be less emphasized, but usually anti addition is dominant.