We report herein on the phosphine-catalyzed
hydrovinylation reaction
by three-component coupling of acyl fluorides, silyl enol ethers,
and alkynoates. The key to the success of the reaction is the formal
transmetalation between pentacoordinate P(V) species (i.e., fluorophosphorane)
and a silyl enol ether, which allows for C–C bond formation
between the polarity-mismatched sites. The bond formation that cannot
be attained even by transition metal catalysis is accomplished by
a P(III)/P(V) manifold.