ACS Catalysis,
Год журнала:
2024,
Номер
15(2), С. 759 - 767
Опубликована: Дек. 25, 2024
A
synthetic
strategy
for
the
catalytic
cycloaddition
of
α-trifluoromethyl-α-diazoketones
with
nitriles
has
been
achieved
based
on
cobalt(II)
metalloradical
catalysis.
The
easily
accessible
starting
materials,
cost-effective
catalyst,
and
experimental
simplicity
rendered
this
protocol
a
robust
practical
approach
to
construct
diverse
functionalized
4-CF3-substituted
oxazoles
high
efficiency.
wide
substrate
scope
both
α-trifluoromethylated
diazoketones
is
amenable
system.
level
functional
group
tolerance
provides
several
opportunities
precise
late-stage
modifications
bioactive
drug-like
molecules.
Mechanistic
experiments
spectroscopic
investigations
confirm
radical
nature
reaction
reveal
involvement
monocarbene
biscarbene
intermediates
during
process.
Molecules,
Год журнала:
2025,
Номер
30(1), С. 183 - 183
Опубликована: Янв. 5, 2025
An
efficient
Rh(III)-catalyzed
C-H
activation
of
azobenzenes
and
subsequent
[4+1]
cascade
annulation
with
CF3-imidoyl
sulfoxonium
ylides
was
developed,
yielding
diverse
CF3-indazoles.
This
protocol
featured
easily
available
starting
materials,
excellent
functional
group
tolerance
high
efficiency.
Moreover,
the
antitumor
activities
selected
CF3-indazoles
against
human
cancer
cell
lines
were
also
studied,
results
indicated
that
several
compounds
displayed
considerable
antiproliferative
activities.
Ring-fluorinated
azaheterocycles
have
wide
applications
in
agrochemicals,
pharmaceuticals,
and
synthesis,
which
prompt
continuous
endeavors
to
expand
such
heterocyclic
families.
However,
monofluorinated
triazaheterocycles
hardly
been
explored.
This
work
reported
a
novel
modular
synthesis
of
1,2,4-triazoles
1,3,5-triazines,
utilizes
N-CF3
imidoyl
chlorides
as
unique
polyfluoro
synthons
their
defluorinative
annulations
with
hydrazines/imidazines.
Further
modifications
these
fluorinated
heterocycles
highlight
the
potential
method
for
accessing
functional
molecules.
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 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
Organic Letters,
Год журнала:
2025,
Номер
27(2), С. 657 - 662
Опубликована: Янв. 7, 2025
A
condition-controlled
Rh(III)-catalyzed
selective
synthesis
of
CF3-substituted
indoles
and
pyrido[2,1-a]isoindoles
from
2-arylpyridines
CF3-imidoyl
sulfoxonium
ylides
has
been
developed.
The
Cp*Rh(MeCN)3(SbF6)2/HFIP
system
afforded
via
triple
C–H
activation,
while
the
[Cp*RhCl2]2/MeCN
condition
selectively
furnished
through
[4
+
1]
annulation.
notable
advantages
this
developed
method
included
readily
available
starting
materials,
broad
substrate
scope,
excellent
chemoselectivity.
Importantly,
several
selected
products
showed
promising
antitumor
activities.
The
defluorination
of
trifluoromethyl
groups
typically
involves
breaking
one
or
all
three
C-F
bonds,
while
selectively
cleaving
exactly
two
bonds
presents
a
considerable
challenge.
In
this
work,
we
present
method
for
the
sequential
hydrazones
under
photocatalytic
conditions,
which
specific
breakage
followed
by
thiolation
to
yield
monofluorinated
alkenes
containing
thiol
group.
Transforming
trifluoromethyl-containing
polyfluoroalkyl
substances
into
fluorinated
non-PFAS
compounds
holds
potential
practical
implications.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(22), С. 5782 - 5804
Опубликована: Янв. 1, 2023
This
feature
article
summarizes
the
developments
in
fluorinated
carbene
transformations,
and
their
consequent
C–F
functionalization
a
cascade
platform.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(11), С. 7982 - 7990
Опубликована: Май 28, 2024
The
synthesis
of
monofluorinated
heterocyclic
compounds
by
C-H
activation
combined
with
defluorination
is
useful.
Studies
on
the
reaction
mechanism
and
selectivity
have
shown
that
these
processes
play
a
positive
role
in
promoting
development
reactions.
Density
functional
theory
(DFT)
calculations
were
performed
to
investigate
Ru(II)-catalyzed
2-arylbenzimidazole
trifluoromethyl
diazo.
DFT
showed
occurs
through
concerted
metalation/deprotonation
(CMD)
mechanism.
After
that,
deprotonation
defluorinative
cyclization
are
assisted
acetate
trifluoroethanol
(TFE).
Further
mechanistic
insights
noncovalent
interaction
(NCI)
analysis
also
obtained
elucidate
origin
process.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(32)
Опубликована: Июнь 12, 2024
Abstract
The
formation
of
carbon‐fluorine
(C−F)
bonds
is
an
important
research
field
in
organic
synthesis
because
inserting
a
fluorine
atom
into
compound
can
alter
its
physicochemical
properties,
such
as
metabolic
stability
and
permeability.
Due
to
this
unique
property,
fluorinated
compounds,
especially
aryl
fluorides,
have
wide
range
applications
various
fields,
including
agrochemicals,
pharmaceuticals,
materials
science.
Therefore,
numerous
metal‐
or
metal‐free‐mediated
fluorination
reactions
been
developed
synthesize
fluorides.
In
mini‐review,
we
summarize
recent
ten
years’
advances
for
the
