The Chemical Record,
Journal Year:
2023,
Volume and Issue:
23(9)
Published: April 18, 2023
Abstract
Carbon‐fluorine
bonds
are
stable
and
have
demonstrated
sluggishness
against
various
chemical
manipulations.
However,
selective
transformations
of
C−F
can
be
achieved
by
developing
appropriate
conditions
as
useful
synthetic
methods
in
organic
chemistry.
This
review
focuses
on
C−C
bond
formation
at
monofluorinated
sp
3
‐hybridized
carbons
via
cleavage,
including
cross‐coupling
multi‐component
coupling
reactions.
The
cleavage
mechanisms
the
carbon
centers
primarily
categorized
into
three
types:
Lewis
acids
promoted
F
atom
elimination
to
generate
carbocation
intermediates;
nucleophilic
substitution
with
metal
or
nucleophiles
supported
activation
coordination
acids;
a
single
electron
transfer.
characteristic
features
alkyl
fluorides,
comparison
other
(pseudo)halides
promising
electrophilic
counterparts,
also
discussed.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(16), P. 2810 - 2814
Published: April 3, 2023
The
elemental
sulfur-mediated
synthesis
of
acyl
fluorides
from
carboxylic
acids
is
achieved
using
Selectfluor.
A
broad
range
are
accessible
while
avoiding
the
formation
acid
anhydrides.
19F
NMR
spectra
suggest
that
S8-fluoro-sulfonium
cation
and
neutral
S8-difluoride
A'
generated
in
situ
reactive
species
this
deoxyfluorination
reaction.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
24(1), P. 385 - 389
Published: Dec. 22, 2021
In
this
Letter,
the
palladium/copper-cocatalyzed
arylsilylation
of
internal
alkynes
with
acyl
fluorides
and
silylboranes
is
described.
This
first
example
in
which
have
been
utilized
for
three-component
coupling
reaction
via
decarbonylation,
yielding
a
variety
tetrasubstituted
alkenylsilanes
moderate
to
good
yields.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(22)
Published: March 30, 2023
Aryl
fluorides
are
expected
to
be
useful
as
radiolabeling
precursors
due
their
chemical
stability
and
ready
availability.
However,
direct
via
carbon-fluorine
(C-F)
bond
cleavage
is
a
challenging
issue
its
significant
inertness.
Herein,
we
report
two-phase
radiosynthetic
method
for
the
ipso-11
C-cyanation
of
aryl
obtain
[11
C]aryl
nitriles
nickel-mediated
C-F
activation.
We
also
established
practical
protocol
that
avoids
use
glovebox,
except
initial
preparation
nickel/phosphine
mixture,
rendering
applicable
general
PET
centers.
This
enabled
efficient
synthesis
diverse
from
corresponding
fluorides,
including
pharmaceutical
drugs.
Stoichiometric
reactions
theoretical
studies
indicated
promotion
effect
lithium
chloride
on
oxidative
addition,
affording
an
aryl(chloro)nickel(II)
complex,
which
serves
precursor
rapid
11
C-cyanation.
Inorganics,
Journal Year:
2023,
Volume and Issue:
11(6), P. 260 - 260
Published: June 19, 2023
Understanding
the
interface
between
soluble
metal
complexes
and
supported
particles
is
important
in
order
to
reveal
reaction
mechanisms
a
new
generation
of
highly
active
homogeneous
transition
catalysts.
In
this
study,
we
show
that,
case
palladium
forming
on
carbon
(Pd/C)
catalyst
from
Pd(0)
complex
Pd2dba3,
nature
deposited
surface
turns
out
be
much
richer
than
previously
assumed,
even
if
very
simple
experimental
procedure
utilized
without
use
additional
reagents
procedures.
process
obtaining
heterogeneous
Pd/C
catalyst,
“hidden”
centers
are
formed
surface,
which
leached
by
solvent
demonstrate
diverse
reactivity
solution
phase.
The
results
indicate
that
catalysts
may
naturally
contain
trace
amounts
molecular
monometallic
different
easily
transforming
them
catalytic
system.
line
with
modern
concept,
heterogenized
precursor
was
found
leach
first,
leaving
nanoparticles
mostly
intact
surface.
point
neglected
soft
leaching
contributes
high
activity.
obtained
demand
for
reconsidered
as
flexible
tool
construction
rational
design
selective
systems,
starting
available
precursors.
The Chemical Record,
Journal Year:
2023,
Volume and Issue:
23(9)
Published: April 18, 2023
Abstract
Carbon‐fluorine
bonds
are
stable
and
have
demonstrated
sluggishness
against
various
chemical
manipulations.
However,
selective
transformations
of
C−F
can
be
achieved
by
developing
appropriate
conditions
as
useful
synthetic
methods
in
organic
chemistry.
This
review
focuses
on
C−C
bond
formation
at
monofluorinated
sp
3
‐hybridized
carbons
via
cleavage,
including
cross‐coupling
multi‐component
coupling
reactions.
The
cleavage
mechanisms
the
carbon
centers
primarily
categorized
into
three
types:
Lewis
acids
promoted
F
atom
elimination
to
generate
carbocation
intermediates;
nucleophilic
substitution
with
metal
or
nucleophiles
supported
activation
coordination
acids;
a
single
electron
transfer.
characteristic
features
alkyl
fluorides,
comparison
other
(pseudo)halides
promising
electrophilic
counterparts,
also
discussed.
