The introduction of allyl fluorides as alternative electrophiles in asymmetric allylic
alkylation reactions has recently attracted significant interest. Despite the intrinsic
thermodynamically demanding C–F bond-cleavage event, the fluorophilic nature of the
silicon atom is key in assisting the activation and cleavage of the allylic C–F bond.
Thus, the use of silylated compounds as unconventional nucleophiles, together with
the Lewis basicity of fluorine when acting as a leaving group, enables the development
of innovative chemical transformations within mild and selective catalytic schemes.
This Synpacts article summarizes the diverse defluorinative asymmetric allylic alkylations
with allyl fluorides reported to date under both chiral Lewis base and transition-metal
catalysis.
Key words
C–F bond activation - defluorination - asymmetric catalysis - allylic alkylation -
Lewis base catalysis - transition-metal catalysis
