ORGN 128

In this study, the reaction of unsaturated alcohols with F-TEDA yields cyclic fluoroethers as well as products (fluoroamides) resulting from solvent (acetonitrile) incorporation.  Also, vinyl fluorides have been observed in some cases. Nitromethane has proven to be the better solvent in the formation of cyclic fluoroethers.  These three types of products are derived from the formation of an intermediate β-fluorocarbocation resulting from the initial electrophilic addition of fluorine to the alkenyl alcohol.  The vinyl fluorides and fluoroamides are formed in direct competition with the intramolecular fluoroalkoxylation to generate cyclic fluoroethers.  These results are consistent with the presence of a fluorocarbocation, which may react either by solvent incorporation, by  intramolecular cyclization or by deprotonation.  In this study, five different starting materials have been used to synthesize  8-, 6-, 5-, and  4-membered cyclic fluoroethers.  Cyclization of β-citronellol produces the 8-membered ring, 6-methyl-5-hepten-2-ol produces the 6-membered ring, trans-3-hexen-1-ol and 5-hexen-1-ol both produce a 5-membered ring, and cinnamyl alcohol produces a 4-membered ring.