Abstract
Radicals
can
be
formed
expeditiously
through
the
direct
irradiation
of
an
electron
donor‐acceptor
(EDA)
complex.
Herein,
we
show
a
photocatalyst‐free
strategy
for
gem
‐difluoroalkenes
synthesis
realized
by
photo‐irradiation
EDA
complexes,
which
generated
in
situ
between
N
‐alkylpyridinium
salts
and
Hantzsch
ester
without
any
other
additives.
A
wide
variety
readily
available
alkylamines
underwent
deaminative
defluoroalkylation
to
provide
corresponding
‐difluoroalkenes.
This
reaction
system
exhibits
high
reactivity
good
functional
group
tolerance
provides
practical
effective
entry
broad
range
α
‐alkyl‐substituted
Green Chemistry,
Год журнала:
2023,
Номер
25(17), С. 6733 - 6738
Опубликована: Янв. 1, 2023
A
metal
free,
visible-light
driven
α-C(sp
3
)−H
gem-difluoroallylation
of
glycine
derivatives
with
CF
-alkenes
and
1,3-enynes
is
presented
under
redox-neutral
conditions
good
yields
excellent
functional
group
compatibility.
Organic Letters,
Год журнала:
2023,
Номер
25(13), С. 2294 - 2299
Опубликована: Март 23, 2023
A
concise
and
efficient
hydrodefluorination
process
was
developed
for
the
synthesis
of
gem-difluoroalkenes.
This
reaction
employs
rongalite
as
a
masked
proton
source
does
not
require
any
additional
catalysts
or
reductants.
Notably,
trifluoromethyl
alkenes
having
both
terminal
internal
double
bonds
are
compatible
with
this
process,
allowing
wider
range
substrates.
The
successful
late-stage
functionalizations
pharmaceuticals
gram-scale
syntheses
were
used
to
demonstrate
viability
method.
Chemical Communications,
Год журнала:
2023,
Номер
59(25), С. 3707 - 3710
Опубликована: Янв. 1, 2023
Radical
defluorinative
functionalization
of
α-trifluoromethyl
styrenes
represents
an
effective
way
toward
gem-difluoroalkenes.
There
are
general
interests
in
developing
novel
synthetic
protocols
for
with
various
types
radicals.
However,
reports
on
the
preparation
gem-difluoro
allylsulfones
via
S-centered
radical
pathway
limited.
Herein,
we
developed
a
photo/nickel
dual-catalyzed
sulfonylation
that
rapidly
and
reliably
synthesizes
allylsulfones.
The
merit
this
protocol
is
exhibited
by
its
mild
conditions
wide
scope,
thus
providing
strategy
sulfonyl
participating
coupling.
Green Chemistry,
Год журнала:
2024,
Номер
26(17), С. 9371 - 9377
Опубликована: Янв. 1, 2024
Defluorinative
alkylation
and
arylation
between
thianthrenium
salts
α-trifluoromethyl
alkene
to
afford
gem
-difluoroolefins
by
easily
recycling
thianthrene
under
visible
light
irradiation
free
of
metal
photocatalyst.
Organic Letters,
Год журнала:
2022,
Номер
24(48), С. 8753 - 8758
Опубликована: Ноя. 28, 2022
The
unprecedented
photochemical
late-stage
defluorinative
gem-difluoroallylation
of
aryl
sulfonium
salts,
which
are
formed
site-selectively
by
direct
C(sp2)─H
functionalization,
is
herein
disclosed.
This
method
distinguished
its
mild
reaction
conditions,
wide
scope,
and
excellent
site-selectivity.
As
showcase
examples,
a
Flurbiprofen
Pyriproxyfen
derivatives
could
be
late
stage
gem-difluoroallylated
with
high
yields.
Experimental
computational
investigations
were
conducted.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(12), С. 1360 - 1366
Опубликована: Фев. 23, 2024
Comprehensive
Summary
The
conversion
of
CF
3
‐alkenes
to
gem
‐difluoroalkenes
using
reductive
cross‐coupling
strategy
has
received
much
attention
in
recent
years,
however,
the
use
green
and
readily
available
reducing
salt
mediate
these
reactions
remains
be
explored.
In
this
work,
a
concise
construction
gem‐
difluoroalkenes,
which
requires
neither
catalyst
nor
metal
agent,
was
established.
Rongalite,
safe
inexpensive
industrial
product,
employed
as
both
radical
initiator
reductant.
This
procedure
compatible
with
linear
cyclic
diaryliodonium
salts,
enabling
wide
variety
substrates
(>70
examples).
utility
approach
demonstrated
through
gram‐scale
synthesis
efficient
late‐stage
functionalizations
anti‐inflammatory
drugs.
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.
Organic Letters,
Год журнала:
2025,
Номер
27(10), С. 2377 - 2382
Опубликована: Март 5, 2025
Direct
gem-difluoroallylation
at
the
α-carbonyl
position
is
a
challenging
process
by
conventional
methods.
Herein
we
report
photocatalytic
radical
α-C(sp3)─H
of
amides
with
trifluoromethyl
alkenes
to
access
target
compounds
good
yields
and
functional
group
tolerance.
The
mild
effective
conditions
allow
gem-difluoroalkene
motifs
as
carbonyl
bioisosteres
incorporated
concisely
some
complex
molecules,
including
gemfibrozil
estrone
derivatives,
presenting
great
potential
for
late-stage
functionalization
drugs,
natural
products,
bioactive
intermediates.
Mechanistic
investigations
suggest
pathway
combining
XAT
1,5-HAT.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(17)
Опубликована: Март 29, 2024
Abstract
gem
‐Difluoroalkenes
are
unique
structural
motifs
with
important
applications
ranging
from
drugs
to
materials.
Herein,
we
report
a
novel
radical‐mediated
defluorinative
allylation
of
sulfamate
esters
through
distal
C(sp
3
)−H
functionalization
under
photoredox
conditions.
The
reaction
could
readily
incorporate
various
‐difluoroalkene
into
previously
unfunctionalized
sp
carbon
centers.
transformation
allows
directly
dual
activation
N−H
and
bonds
via
photocatalytic
redox‐neutral
process,
as
well
using
water
environmentally
friendly
co‐solvent.
provide
general
operationally
simple
method
access
compounds
high
diversity.
