Abstract
Dehydrochlorination
(DHC)
is
of
importance
for
modulating
the
physical
properties
halogenated
polymers.
In
this
work,
DHC
commercial
VDF‐CTFE
(vinylidene
fluoride‐co‐chlorotrifluoroethylene)
(10
mol
%
CTFE)
copolymer
to
VDF‐DB
fluoride
with
unsaturated
moieties‐
D
ouble
B
ond)
was
achieved
in
mild
reaction
conditions
(150
°C
and
3
bar
hydrogen)
using
different
supported
nickel
catalysts.
A
complete
observed
within
four
hours
reaction.
Additionally,
a
certain
extent
(8–35
%)
hydrodefluorination
(HDF)
polymer,
challenging
transformation,
can
also
be
after
72
hours.
plausible
mechanism
based
on
nuclear
magnetic
resonance
(NMR)
spectroscopy
study
HDF
proposed.
The
catalyst
recyclable
stable
against
leaching
at
least
three
cycles.
ACS Catalysis,
Год журнала:
2023,
Номер
13(18), С. 12238 - 12268
Опубликована: Сен. 1, 2023
Organofluorine
compounds
have
attracted
extensive
attention
in
various
industrial
fields
due
to
their
unique
chemical
and
physical
properties.
Despite
increasing
demand
a
wide
range
of
scientific
fields,
the
synthesis
organofluorine
still
faces
several
problems,
such
as
difficulties
handling
fluorinating
reagents
control
chemoselectivity.
Compared
with
formation
C–F
bonds,
activation
functionalization
carbon–fluorine
bonds
is
very
important
but
challenging
topic
synthetic
chemistry.
Due
properties
nickel,
Ni-catalyzed
defluorinative
cross-couplings
been
greatly
developed
past
few
decades
powerful
strategies
for
construction
fluorinated
organic
compounds.
This
Review
summarizes
advances
cross-coupling
aryl
fluorides,
gem-difluorovinyl
trifluoromethyl
Advanced Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 31, 2024
Abstract
Introducing
distinctive
functional
groups
to
expand
the
structural
diversity
and
improve
intrinsic
properties
of
parent
molecules
has
been
an
essential
pursuit
in
organic
chemistry.
By
using
perfluoroalkyl
halide
(PFAH)
as
a
nontraditional,
readily
available,
ideal
1,2‐difluoroalkenyl
coupling
partner,
defluorinative
cyclization
reaction
enamides
for
construction
fluoroalkenyl
oxazoles
is
first
developed.
The
selective
controllable
two‐fold
cleavage
vicinal
C(sp
3
)─F
bonds
PFAH
not
only
enables
introduction
specific
moiety
with
ease
but
also
results
functionalization
two
2
)─H
without
need
metal
catalyst,
photocatalyst,
oxidant,
or
light.
method
can
be
applied
late‐stage
modification
complex
molecules,
synthesis
biological‐relevant
oxazole
analoges,
scale‐up
synthesis,
which
all
further
highlight
real‐world
utility
this
protocol.
Mechanistic
studies
reveal
that
possibly
proceeds
through
radical
perfluoroalkylation,
consecutive
C─F
bond
heterolytic
cleavage,
process.
In
addition,
situ
formed
may
serve
hydrogen
abstractor.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(40)
Опубликована: Авг. 19, 2023
Abstract
An
α‐difluoroalkylation
of
benzyl
amines
with
trifluoromethylarenes
is
disclosed
herein.
This
protocol
characterized
by
its
operational
simplicity,
excellent
chemoselectivity
and
broad
scope—even
advanced
synthetic
intermediates—,
thus
offering
a
new
entry
point
to
medicinally‐relevant
α‐difluoroalkylated
from
simple,
yet
readily
accessible,
precursors.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(5), С. 1388 - 1394
Опубликована: Янв. 1, 2024
Zn-catalyzed
stereoselective
hydrodefluorination
of
CF
3
-substituted
alkenes,
gem
-difluoroalkenes
and
polyfluoroarenes
by
hydride
ion
addition
has
been
realized
through
controlled
C(sp
)–F
and/or
2
bonds
cleavage.
Organic Letters,
Год журнала:
2024,
Номер
26(4), С. 928 - 932
Опубликована: Янв. 25, 2024
Perfluoroalkyl
compounds
are
persistent
environmental
pollutants
due
to
their
chemical
and
thermal
stability.
Hydrodefluorination
is
one
of
the
most
promising
strategies
for
disposal
fluorine-containing
compounds,
which
has
attracted
much
attention
from
a
broad
spectrum
scientific
communities.
Herein,
we
disclose
metal-free,
visible-light-promoted
protocol
exhaustive
hydrodefluorination
wide
variety
trifluoromethylarenes
with
up
95%
yields.
Moreover,
methyl-d3
groups
can
be
obtained
via
deuterium
water
D
ratio
94%.
Abstract
Efficient
Ni‐catalyzed
hydrodehalogenations
and
deuterodehalogenations
of
aryl/heteroaryl
halides
are
reported
herein.
This
new
technology
can
be
used
to
incorporate
not
only
hydrogen,
but
also
deuterium
into
various
aromatic/heteroaromatic
compounds
with
high
efficiency,
using
2–6
mol
%
nickel
in
the
presence
stoichiometric
NaBH
4
.
Over
40
examples
have
been
successfully
converted
corresponding
(hetero)arenes
excellent
yields.
The
process
is
conducted
under
green
chemistry
conditions:
water
enabled
by
designer
surfactants,
a
medium
which
readily
recycled.
Minimal
organic
solvent,
needed
given
small
(academic)
scale
reactions,
for
product
isolation,
resulting
low
E‐Factors.
Additionally,
sterically
hindered
substrates
amenable,
as
selected
APIs
that
feature
carbon‐fluorine
bonds.
Organic Letters,
Год журнала:
2023,
Номер
25(29), С. 5548 - 5551
Опубликована: Июль 18, 2023
Functionalization
of
perfluoroalkyl
compounds
has
shown
huge
potential
in
synthetic
chemistry
and
drug
development.
Herein,
we
report
a
one-pot
tandem
perfluoroalkylation-defluorination
reaction
indole,
iodide,
water
the
presence
Na2S2O4.
A
wide
array
indole
derivatives
were
efficiently
accessed
with
good
yields
under
mild
conditions.
The
is
believed
to
undergo
perfluoroalkylation
follow
defluorination
hydrolysis
pathway.
This
study
represents
an
alternative
approach
for
functionalization.
