Chemical Communications,
Год журнала:
2022,
Номер
59(4), С. 486 - 489
Опубликована: Дек. 16, 2022
The
Pd-catalyzed
highly
selective
synthesis
of
mono-
and
di-2-fluoroallylic
amines
from
gem-difluorocyclopropanes
ubiquitous
unprotected
primary
anilines
is
herein
described.
Initial
kinetic
investigations
suggest
a
first
order
in
the
gem-difluorocyclopropane
substrate,
as
well
circa
zeroth
aniline
coupling
partner.
newly
produced
fluoroallylic
motifs
should
find
important
applications
synthetic
medicinal
chemistry
stimulate
further
development
methods
based
on
strained
cyclic
building
blocks.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
89(22), С. 16253 - 16261
Опубликована: Сен. 22, 2023
Monofluoroalkene
scaffolds
are
frequently
found
in
various
functional
molecules.
Herein,
we
report
a
Pd-IHept-catalyzed
(NHC
=
N-heterocyclic
carbene)
defluorinative
functionalization
approach
for
the
synthesis
of
monofluoroalkenes
from
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
42(8), С. 823 - 828
Опубликована: Дек. 8, 2023
Comprehensive
Summary
Herein,
we
report
nickel‐catalyzed
cross‐coupling
of
gem
‐difluorinated
cyclopropanes
with
boronic
acids,
providing
the
corresponding
arylated
2‐fluoroallylic
scaffolds.
This
approach
used
commercially
available
phosphine
ligand
Xantphos
to
obtain
monofluorinated
alkenes
high
regioselectivity
and
Z
‐stereoselectivity.
Mechanistic
studies
proposed
a
Ni(II)‐fluoroallyl
pathway
excluded
radical
pathway.
Meanwhile,
DFT
study
reductive
elimination
clarified
origin
linear
selectivity.
Herein,
we
report
a
Rh-catalyzed
carbofluorination
of
alkenes
using
gem-difluorinated
cyclopropanes
as
bifunctional
reagents.
The
developed
method
tolerates
wide
range
alkenes,
providing
access
to
secondary,
tertiary
fluorides
and
gem-difluorides
with
100%
atom-economy
under
mild
conditions.
resulting
can
be
further
transformed
yield
C−C,
C−N,
C−O
bifunctionalization
products.
Cationic
dicarbonyl
rhodium
tetrafluoroborate
has
been
identified
the
only
highly
efficient
catalyst
in
this
reaction.
Preliminary
mechanistic
studies
reveal
that
addition
fluorine
atom
is
mediated
by
ion,
which
acts
anion
shuttle.
Chemical Communications,
Год журнала:
2022,
Номер
59(4), С. 486 - 489
Опубликована: Дек. 16, 2022
The
Pd-catalyzed
highly
selective
synthesis
of
mono-
and
di-2-fluoroallylic
amines
from
gem-difluorocyclopropanes
ubiquitous
unprotected
primary
anilines
is
herein
described.
Initial
kinetic
investigations
suggest
a
first
order
in
the
gem-difluorocyclopropane
substrate,
as
well
circa
zeroth
aniline
coupling
partner.
newly
produced
fluoroallylic
motifs
should
find
important
applications
synthetic
medicinal
chemistry
stimulate
further
development
methods
based
on
strained
cyclic
building
blocks.
