Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(38)
Published: Aug. 3, 2023
Abstract
Aliphatic
trifluoromethyl
ketones
are
a
type
of
unique
fluorine‐containing
subunit
which
play
significant
role
in
altering
the
physical
and
biological
properties
molecules.
Catalytic
methods
to
provide
direct
access
aliphatic
highly
desirable
yet
remain
underdeveloped,
partially
owing
high
reactivity
instability
trifluoroacetyl
radical.
Herein,
we
report
photocatalytic
synthesis
from
alkyl
bromides
with
trifluoroacetic
anhydride.
The
reaction
features
dual
visible‐light
halogen‐atom‐transfer
catalysis,
followed
by
an
enabling
radical‐radical
cross‐coupling
radical
stabilized
provides
straightforward
readily
available
cost‐effective
halides
anhydride
(TFAA).
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(7), P. 4199 - 4208
Published: Jan. 1, 2024
A
new
photoelectrocatalytic
mode
permits
the
synthesis
of
polycyclic
pyrimidin-4-ones
through
dehydrogenative
cyclization
malonates
with
unactivated
alkenes.
The Chemical Record,
Journal Year:
2023,
Volume and Issue:
23(9)
Published: May 22, 2023
Abstract
In
the
last
few
years,
many
reagents
and
protocols
have
been
developed
to
allow
for
efficient
fluorofunctionalization
of
a
diverse
set
scaffolds
ranging
from
alkanes,
alkenes,
alkynes,
(hetero)arenes.
The
concomitant
rise
organofluorine
chemistry
visible
light‐mediated
synthesis
synergistically
expanded
fields
mutually
benefitted
developments
in
both
fields.
this
context,
light
driven
formations
radicals
containing
fluorine
major
focus
discovery
new
bioactive
compounds.
This
review
details
recent
advances
progress
made
fluoroalkylation
heteroatom
centered
radical
generation.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(38)
Published: Aug. 3, 2023
Aliphatic
trifluoromethyl
ketones
are
a
type
of
unique
fluorine-containing
subunit
which
play
significant
role
in
altering
the
physical
and
biological
properties
molecules.
Catalytic
methods
to
provide
direct
access
aliphatic
highly
desirable
yet
remain
underdeveloped,
partially
owing
high
reactivity
instability
trifluoroacetyl
radical.
Herein,
we
report
photocatalytic
synthesis
from
alkyl
bromides
with
trifluoroacetic
anhydride.
The
reaction
features
dual
visible-light
halogen-atom-transfer
catalysis,
followed
by
an
enabling
radical-radical
cross-coupling
radical
stabilized
provides
straightforward
readily
available
cost-effective
halides
anhydride
(TFAA).
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(18), P. 12935 - 12948
Published: Sept. 6, 2023
An
electrochemical
or
photoelectrochemical
regioselective
polyfluoroalkylation/cyclization
cascade
of
3-aza-1,5-dienes
with
sodium
fluoroalkanesulfinates
is
presented.
This
protocol
proceeds
a
broad
substrate
scope
and
good
functional
group
tolerance
under
mild,
oxidant-free,
transition-metal-free,
electrolyte-free
conditions
to
provide
3-polyfluoroalkylated
4-pyrrolin-2-ones
in
one
step
from
readily
available
N-vinylacrylamides,
it
scalable
the
Gram
scale.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(24), P. 5196 - 5201
Published: June 10, 2024
A
novel
strategy
for
incorporating
a
trifluoroacetyl
functionality
into
range
of
structurally
varied
unsaturated
bonds
was
developed
by
using
PhI(OCOMe)2
as
an
oxidant
with
masked
trifluoroacyl
reagent
radical
precursor.
The
oxidative
decarboxylation
the
precursor
followed
tandem
process
provides
versatile
access
to
5-exo-trig
cyclization
N-arylacrylamides,
direct
C(sp2)–H
trifluoroacetylation
quinolines,
isoquinoline,
2H-indazole,
and
quinoxalin-2(1H)-ones,
C(sp)–H
alkynes.
This
protocol
is
characterized
mild
reaction
conditions,
operational
simplicity,
broad
functional
group
compatibility.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 14, 2025
We
report
herein
a
method
of
substrate-controlled
pentafluorosulfanylation
activated
alkenes
containing
the
benzimidazole
moiety
with
SF5Cl,
which
provides
highly
efficient
way
to
access
SF5-containing
benzo[4,5]imidazole[2,1-a]isoquinolin-6(5H)-ones,
as
well
N-benzoyl
benzimidazoles.
Besides
pentafluorosulfanyl
group
(-SF5),
current
can
be
applied
tetrafluorosulfanyl
(-SF4-)
incorporation.
A
radical
mechanism
involving
single
electron
transfer
(SET)
or
atom
addition
(ATRA)
process
is
proposed.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 15, 2025
The
integration
of
trifluoroacetyl
(CF3CO)
groups
into
organic
skeletons
is
a
key
research
topic
in
synthetic
chemistry
given
their
significant
potential
to
boost
biological
activity.
Despite
recent
developments
strategies
for
incorporating
moiety
via
radical
intermediates,
the
practical
utilization
inexpensive
and
readily
available
trifluoroacetic
acids
as
sources
has
not
yet
been
developed.
Herein,
an
electrochemical
strategy
employed
achieve
deoxygenative
transformation
directly
with
assistance
PPh3.
obtained
radicals
are
then
coupled
sulfoximine
species,
thus
enabling
synthesis
N-trifluoroacetylated
sulfoximines.
Additionally,
other
fluorinated
alkyl
carboxylic
acids,
including
perfluoro-,
difluoro-,
trifluoromethylcarboxylic
can
also
be
efficiently
utilized
under
these
conditions,
leading
corresponding
acylated
Moreover,
trifluoroacetylation
drug-based
molecules
easy
execution
scale-up
experiments
highlight
applicability
this
protocol.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 13, 2025
The
1,1,2-trifluoroethyl
substituent
should
have
considerable
potential
in
the
design
of
new
biologically
active
molecules,
combining
beneficial
qualities
a
more
metabolically
stable
CH2F
and
positive
electron-withdrawing
impact
fluoroalkyl
substituent.
A
synthetic
source
has
now
been
designed,
synthesized,
utilized.
Thus,
synthesis
diphenyl(1,1,2-trifluoroethyl)sulfonium
trifluoromethanesulfonate
its
use
direct
incorporation
into
variety
organic
molecules
via
visible
light/photoredox
nucleophilic
chemistry
is
reported
this
paper.
Frontiers in Chemistry,
Journal Year:
2025,
Volume and Issue:
13
Published: May 14, 2025
Trifluoromethylation
stands
as
a
pivotal
technology
in
modern
synthetic
chemistry,
playing
an
indispensable
role
drug
design,
functional
material
development,
and
agrochemical
innovation.
With
the
growing
emphasis
on
green
chemistry
principles,
pursuit
of
environmentally
benign
trifluoromethylation
strategies
has
emerged
critical
research
frontier.
Trifluoroacetic
acid
(TFA),
characterized
by
its
cost-effectiveness,
stability,
low
toxicity,
become
promising
alternative
to
conventional
reagents.
This
review
systematically
summarizes
advancements
photocatalytic
decarboxylative
using
TFA
derivatives
over
past
decade,
focusing
three
key
activation
mechanisms:
single-electron
transfer
(SET),
electron
donor-acceptor
(EDA)
complex-mediated
pathways,
ligand-to-metal
charge
(LMCT).
paradigm
shift
is
driven
intrinsic
limitations
thermal
decarboxylation,
particularly
reliance
harsh
conditions
significant
environmental
burdens.
In
contrast,
enable
efficient
C–CF
3
bond
construction
under
mild
conditions,
offering
modular
platform
for
synthesizing
fluorinated
molecules.
Strategic
priorities
should
focus
overcoming
fundamental
challenges,
including
but
not
limited
optimizing
photosensitizer
catalytic
efficiency,
establishing
regioselective
manipulation
strategies,
engineering
multicomponent
tandem
reaction
systems
achieve
methodologies
conditions.
Furthermore,
integration
mechanistic
investigations
with
artificial
intelligence-driven
prediction
will
accelerate
advancement
precision
technologies.
progress
anticipated
provide
sustainable
solutions
next-generation
pharmaceuticals
advanced
materials,
effectively
bridging
innovation
gap
between
academic
industrial
implementation.
