We
herein
report
a
photochemical
Truce–Smiles
rearrangement
reaction
of
N-sulfinyl
acrylamides
with
bromodifluoroacetamides
resulting
in
the
synthesis
series
aryl
difluoroglutaramides
moderate
to
good
yields.
The
asymmetric
using
chiral
sulfinamides
produced
quaternary
carbon-centered
glutaramide
products
modest
enantioselectivity.
This
protocol
effectively
complements
previous
methods
involving
N-sulfonyl
acrylamides.
A
photocatalytic
methodology
for
the
chemodivergent
direct
cross-coupling
of
simple
alkanes
with
trifluoromethyl
alkenes
that
enables
selective
formation
gem
-difluoroalkenes
and
is
presented.
JACS Au,
Год журнала:
2025,
Номер
5(2), С. 466 - 485
Опубликована: Фев. 7, 2025
Fluorinated
molecules
are
of
paramount
importance
because
their
unique
properties.
As
a
result,
the
search
for
innovative
approaches
to
synthesis
this
class
compounds
has
been
relentless
over
years.
Among
these,
combination
photocatalysis
and
organofluorine
chemistry
turned
out
be
an
effective
partnership
access
unattainable
fluorinated
molecules.
This
Perspective
provides
overview
recent
advances
in
synthesizing
via
organophotoredox-catalyzed
defluorination
process
from
trifluoromethylated
compounds.
It
encompasses
preparation
difluoromethylated
(hetero)arenes,
amides,
esters
as
well
gem-difluoroalkene
derivatives
using
C(sp3)–F
bond
activation
or
β-fragmentation.
will
highlight
remaining
challenges
discuss
future
research
opportunities.
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
transition-metal-free
protocol
for
the
unsymmetrical
radical
1,3-difunctionalization
of
alkenes
has
been
established
first
time
in
form
1,3-difluoroalkylcarboxylation
by
a
photocatalytic
three-component
reaction
allyl
formates,
trifluoroacetanilides,
and
cesium
formate.
This
employs
formate
as
carboxylating
reagent
trifluoroacetanilide
difluoroalkylating
via
C-F
bond
activation.
As
result,
series
previously
inaccessible
difluorinated
adipic
acid
derivatives
can
be
easily
efficient
prepared.
Mechanism
studies
reveal
that
triple
kinetic-controlled
self-ordering
is
key
to
this
unique
reaction.
sorting
involves
fast
initiation
CO2
anion
its
chemoselective
addition
reduction,
followed
slow
generation
fluoroalkyl
chemo-/regioselective
addition.
Notably,
strategy
also
suitable
cyclic
through
diastereoselectively
constructing
two
or
three
consecutive
stereocenters.
Advanced Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 25, 2025
Abstract
The
introduction
of
F‐containing
groups
into
organic
molecules
can
significantly
alter
their
physical
and
chemical
properties.
Particularly,
gem
‐difluoroalkenes
serve
as
versatile
precursors
for
a
broad
variety
organofluorine
compounds,
commonly
used
in
agrochemicals,
pharmaceuticals,
materials
science.
Based
on
the
kinetics
H•
transfer
to
acrylamide
(
k
H
=
2.28
×
10
−4
M
−1
s
at
300
K
toluene),
study
describes
nickel‐hydride‐(or
Li[BEt
3
H])
initiated
hydrocyclization/defluorination
CF
‐substituted
acrylamides,
offering
alternative
access
4‐fluorovinyl‐substituted
2‐pyrrolidones
(Seletracetam
derivatives
that
are
antiepileptic
drug
candidates).
This
process
proceeds
with
high
yields
remarkable
chemo‐
regioselectivity.
be
by
either
or
–
transfer,
followed
5‐exo‐trig
cyclization
subsequent
fluorine
elimination.
strategy
has
been
applied
late‐stage
functionalization
molecules,
providing
valuable
tool
synthesis
pharmaceutical
compounds.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(8), С. 5619 - 5633
Опубликована: Апрель 5, 2024
Hydroxanthones
have
attracted
considerable
attention
due
to
their
significance
in
organic
and
biological
chemistry,
yet
synthesis
remains
a
great
challenge.
In
this
study,
series
of
chromone-tethered
alkenes
are
designed,
radical
cyclization
reaction
these
chromone
derivatives
has
been
achieved
under
photoredox
conditions.
The
uses
bromodifluoroacetamides
or
bromodifluoroacetates
as
coupling
partners,
affording
broad
range
functionalized
tetrahydroxanthone
products
with
up
85%
yields.
is
triggered
via
the
generation
difluoroacetate
radicals
alkene
cations
fac-Ir(ppy)3
2,3,5,6-tetrakis(carbazol-9-yl)-1,4-dicyanobenzene
photocatalyst.
This
approach
offers
access
various
from
readily
available
starting
materials
enriches
research
content
heteroarene-tethered
alkenes.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(12), С. 8342 - 8356
Опубликована: Май 31, 2024
A
mild
and
transition-metal-free
defluorinative
alkylation
of
benzyl
amines
with
trifluoromethyl
alkenes
is
reported.
The
features
this
protocol
are
easy-to-obtain
starting
materials,
a
wide
range
substrates,
functional
group
tolerance
as
well
high
atom
economy,
thus
offering
strategy
to
access
variety
Green Chemistry,
Год журнала:
2024,
Номер
26(15), С. 8694 - 8700
Опубликована: Янв. 1, 2024
Visible-light-induced
hydroxycarboxylation
of
α-trifluoromethylstyrenes
under
an
air
atmosphere
was
developed
to
construct
densely
functionalized
α-CF
3
tertiary
alcohols.
Chemistry - An Asian Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 11, 2024
β-(Trifluoromethyl)styrenes
are
potentially
useful
building
blocks
for
the
synthesis
of
organofluorine
compounds
because
their
electron-deficient
C=C
double
bonds
can
undergo
diverse
transformations.
One
most
practical
methods
preparing
β-(trifluoromethyl)styrenes
is
decarboxylative
trifluoromethylation
readily
available
cinnamic
acid
derivatives
using
Langlois
reagent
as
a
less
expensive
trifluoromethyl
source.
We
revisited
electrochemical
to
identify
modified
conditions
that
reduce
loading
without
additional
additives.
The
reaction
mechanism
was
computationally
investigated
gain
insight
into
dependence
product
yields
on
aryl
terminal
groups.
synthetic
utility
obtained
demonstrated
by
transformation
4-aryl-3-(trifluoromethyl)pyrrolidines.
