Abstract
The
difluoromethyl
group
(CF2H)
can
function
as
a
lipophilic
hydrogen-bond
donor,
and
is
regarded
bioisostere
of
functional
groups
such
hydroxy
(-OH),
thiol
(-SH),
amino
(-NH2).
unique
physicochemical
properties
this
make
difluoromethylation
hot
topic
in
the
field
synthetic
organic
chemistry,
recent
decades,
various
methods
have
been
developed
for
constructing
C(sp3)—CF2H,
C(sp2)—CF2H,
C(sp)
—CF2H,
X—CF2H
(X
=
N,
O,
S,
Se,
B,
P,
etc.)
bonds.
This
review
summarizes
currently
available
reagents
performing
reactions,
well
other
approaches
installing
unit.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 23, 2025
Herein,
a
N-phenylphenothiazine-based
hyper-cross-linked
polymer
(PTH-HCP)
was
finely
designed
and
constructed,
which
serves
as
metal-free
heterogeneous
photocatalyst
for
organic
transformations.
Characterization
experiments
have
shown
that
this
demonstrates
outstanding
stability,
extensive
surface
area,
exceptional
photoelectric
response
properties.
Moreover,
PTH-HCP
showed
good
catalytic
efficiency
recyclability
in
the
photochemically
driven
difluoromethylation/cyclization
reactions.
This
work
provides
strategy
design
construction
of
photocatalysts
offers
support
their
broad
prospects
synthetic
applications.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(31)
Published: June 5, 2024
Abstract
During
the
past
decade,
radical
difluoromethylation
has
emerged
as
a
powerful
and
versatile
tool
for
incorporation
of
difluoromethyl
into
various
organic
compounds.
These
reactions
feature
mild
reaction
conditions,
very
good
functional
group
compatibilities,
quite
broad
substrate
scopes,
thus
having
drawn
much
attention
got
rapid
developments.
A
diverse
range
precursors
have
been
developed
series
reactions.
This
review
summarizes
discusses
advance
in
reactions,
which
are
organized
according
to
protocols
generating
radical.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 10, 2025
This
study
describes
an
efficacious
and
generally
applicable
synthetic
strategy
for
the
incorporation
of
biologically
physiologically
prominent
difluoromethyl
entity
into
synthetically
crucial
hydrazone
scaffolds
with
bench-stable
easily
accessible
difluoromethyltriphenylphosphonium
bromide.
The
broad
substrate
scope,
excellent
functional
group
compatibility,
feasibility
step
atom
economical
one-pot
manipulation,
environmentally
benign
mild
reaction
conditions
rendered
this
methodology
efficient
tool
preparation
pharmaceutically
fluorine-containing
imino
compounds.
Chemical Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 22, 2025
Fluorine
and
nitrogen
form
a
successful
partnership
in
organic
synthesis,
medicinal
chemistry,
material
sciences.
Although
fluorine-nitrogen
chemistry
has
long
rich
history,
this
field
received
increasing
interest
made
remarkable
progress
over
the
past
two
decades,
driven
by
recent
advancements
transition
metal
organocatalysis
photochemistry.
This
review,
emphasizing
contributions
from
2015
to
2023,
aims
update
state
of
art
synthesis
applications
nitrogen-based
organofluorine
functional
molecules
chemistry.
In
dedicated
sections,
we
first
focus
on
fluorine-containing
reagents
organized
according
type
groups
attached
nitrogen,
including
N-F,
N-RF,
N-SRF,
N-ORF.
review
also
covers
nitrogen-linked
building
blocks,
catalysts,
pharmaceuticals,
agrochemicals,
underlining
these
components'
broad
applicability
growing
importance
modern
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(21), P. 2819 - 2824
Published: June 25, 2023
Comprehensive
Summary
Due
to
its
unique
electronic
properties,
the
difluoromethylene
group
(CF
2
)
has
served
as
a
valuable
unity
in
design
of
biologically
active
molecules.
Since
γ‐lactones
display
broad
range
biological
α,α‐difluoro‐γ‐lactones
may
exhibit
unexpected
activities,
and
thus
their
synthesis
received
increasing
attention.
Traditional
synthetic
methods
suffer
from
tedious
multi‐
step
processes,
very
few
effective
have
been
reported
recently.
Herein,
we
describe
difunctionalization
alkenes
with
BrCF
CO
K
under
photoredox
catalysis
use
boron‐Lewis
acid
for
access
α,α‐difluoro‐γ‐lactones.
In
this
transformation,
alkene
substrates
used
reagents,
including
acid,
PhB(OH)
or
BF
3
·THF,
are
cheap
widely
available.
High
efficiency
atom
economy
make
protocol
attractive.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(14), P. 10206 - 10211
Published: July 12, 2023
The
photoredox-catalyzed
1,6-difluoromethylation
of
3-methyl-4-nitro-5-styrylisoxazole
with
HCF2SO2Na
has
been
developed.
Structurally
diverse
difluoromethylated
products
were
obtained
in
good
yields,
and
their
further
transformations
also
investigated.
di-,
tri-,
monofluoromethylation
the
substrates
compared,
yield
difluoromethylation
was
highest.
DFT
calculations
revealed
that
reaction
CF2H
radical
nucleophilic,
transition
state
activation
energy
lowest.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(4), P. 2525 - 2537
Published: Feb. 1, 2024
Difluoromethylated
compounds
usually
act
as
bioisosteres
for
alcohol
functional
groups
and
show
unique
physicochemical
biological
properties.
The
cyano-difluoromethylation
of
alkenes
using
5-((difluoromethyl)sulfonyl)-1-phenyl-1H-tetrazole
a
CF2H
radical
difluoromethyl
precursor
was
developed
to
afford
nitriles
including
group.
A
low-cost,
stable,
easily
handled
5-((difluoromethyl)sulfonyl)-1-methyl-1H-tetrazole
(DFSMT)
synthesized
applied
the
reagent.
Using
DFSMT
precursor,
oxyl-difluoromethylation
obtain
difluoromethylated
ether
products.
All
reactions
showed
good
group
tolerability.
Initial
mechanistic
experiments
indicated
that
involved
key
active
intermediate.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(46), P. 9897 - 9902
Published: Nov. 9, 2024
A
new
method
uses
metal
Lewis
acids
as
catalysts
to
convert
sulfonyl
fluorides,
fluorosulfates,
and
sulfamoyl
fluorides
with
silyl
amines
into
S-N
bond-containing
compounds
via
sulfur
fluoride
exchange.
The
reaction
successfully
employs
Ca(NTf
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(18), P. 13457 - 13471
Published: Sept. 3, 2024
Organic
molecules
containing
a
difluoroalkyl
group
are
valuable
and
versatile
chemicals
because
of
their
unique
physicochemical
biological
properties.
Accordingly,
the
development
efficient
practical
difluoroalkylation
for
preparation
these
compounds
is
important
attractive.
Herein,
we
demonstrate
photoredox-catalyzed
base-dependent
selective
carbodifluoroalkylation
halodifluoroalkylation
alkenes
using
readily
available
2-(allyloxy)arylaldehydes
[or
2-(allylamino)arylaldehydes]
XCF
