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.
Catalysis Science & Technology,
Год журнала:
2024,
Номер
14(18), С. 5143 - 5160
Опубликована: Янв. 1, 2024
This
review
article
summarizes
the
visible
light
mediated
synthesis
of
allenes
from
substrates
like
1,3-enynes,
propargylic
carbonates,
homopropargylic
alcohols,
oxalates,
alkynyl
diazo
compounds,
and
terminal
aziridines.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
We
present
a
highly
efficient
and
versatile
nickel-catalyzed
protocol
for
the
reductive
cross-coupling
of
unactivated
CF2H-substituted
electrophiles
with
wide
variety
aryl
alkenyl
halides.
This
novel
approach
offers
high
catalytic
reactivity
broad
functional
group
compatibility,
enabling
late-stage
fluoroalkylation
drug
molecules.
Described
herein
is
the
trimethylsilylation
of
various
nucleophiles
using
a
combination
HCF3
and
NaHMDS.
This
facile
protocol
enables
rapid
construction
alkynylsilanes,
silyl
enol
ethers,
etc.,
under
mild
conditions.
Detailed
mechanistic
studies
indicate
that
trimethylsilicon
intermediate
formed
in
situ
can
be
readily
attacked
by
nucleophiles,
with
activation
base
NaHMDS
difluorocarbene.
work
first
utilizes
structure
HMDS
as
silicon
source
terminal
alkynes.
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.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Май 15, 2025
The
use
of
metal
for
catalytic
difluorocarbene
transfer
reactions
has
long
been
hindered
by
the
lack
understanding
chemistry,
despite
potential
implications
medicinal
chemistry
and
advanced
materials
science.
Here,
we
report
a
copper-catalyzed
reaction
via
1,1-migration
copper
difluorocarbene,
in
contrast
to
previous
nucleophilic
addition
pathway.
This
enables
development
modular
gem-difluoropropargylation
using
variety
simple
widely
available
potassium
propiolates,
terminal
alkynes,
allyl/propargyl
electrophiles
couple
opening
an
avenue
precise
synthesis
organofluorine
compounds
without
tedious
synthetic
procedures.
impact
this
protocol
is
demonstrated
efficient
complex
fluorinated
skeletons
rapid
key
intermediates
pheromone
derivatives
PGF2
agonists.
Mechanistic
studies
reveal
that
migratory
insertion
into
C-Cu
bond
alkynylcopper
species
step
reaction.
The
difluoromethyl
group
(CF2H)
is
an
important
motif
in
medicinal
chemistry.
We
report
the
efficient
synthesis
of
a
range
optically
pure
α-difluoromethyl
amines
via
copper-catalyzed
regio-
and
enantioselective
hydroamination
gem-difluoroalkenes.
application
chiral
pyridine-derived
ligand
inhibits
β-F
elimination
from
α-CF2H
organocopper
intermediate.
proposed
Cu
catalyst
promotes
production
by
Cu-H
insertion
reductive
C-N
bond
using
readily
available
materials.
findings
this
study
establish
new
synthetic
strategy
to
access
motifs.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 29, 2025
Comprehensive
Summary
Aminosilylalkanes
are
important
motifs
in
bioactive
molecules,
yet
methods
for
their
direct
incorporation
remain
limited.
In
particular,
the
efficient
introduction
of
gem
‐difluoro
groups–known
to
significantly
modulate
physical,
chemical,
and
biological
properties
organic
molecules–into
aminosilylalkane
remains
a
challenge.
Herein,
we
report
cobalt‐catalyzed
silyldifluoromethylamination
styrenes
using
TMSCF
2
H
nitrogen
nucleophiles.
By
employing
readily
available
starting
materials,
series
complex,
highly
functionalized
aminosilyldifluoroalkane
derivatives
were
synthesized
moderate
good
yields.
This
methodology
establishes
novel
strategy
constructing
organosilicon
compounds,
complementing
existing
synthetic
approaches.
