cs6b00866_si_001.pdf (8.86 MB)
Autocatalytic Friedel–Crafts Reactions of Tertiary Aliphatic Fluorides Initiated by B(C6F5)3·H2O
journal contribution
posted on 2016-05-04, 00:00 authored by Marian Dryzhakov, Joseph MoranThe
C–F bond is the strongest single bond to carbon, constituting
an intrinsic challenge for selective catalytic activation in the presence
of other functional groups. Existing methods for the activation of
tertiary aliphatic fluorides involve stoichiometric abstraction with
fluorophilic Lewis acids or by Lewis-acid-catalyzed trapping with
Si reagents. Herein, we describe a B(C6F5)3·H2O-catalyzed Friedel–Crafts reaction
of tertiary alkyl fluorides that proceeds rapidly at room temperature
without trapping reagents. The method is completely selective for
F– over traditionally better leaving groups and
displays an autocatalytic kinetic profile.