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.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(11), С. 7586 - 7591
Опубликована: Май 1, 2023
An
alkyl
radical-triggered
dual
C–F
bond
cleavage
of
α-CF3-ortho-hydroxystyrenes
for
the
synthesis
2-fluorobenzofurans
was
developed.
The
visible-light-induced
defluorinative
cross-coupling
reactions
with
a
variety
carboxylic
acids
produced
gem-difluoroalkenes,
which
underwent
SNV-type
5-endo-trig
cyclization
to
give
2-fluorobenzofurans.
Mechanistic
studies
indicated
that
electron
transfer
between
phenoxyl
radicals
and
carboxylates
major
pathway
generation
radicals.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(5), С. 1305 - 1313
Опубликована: Янв. 1, 2024
A
conceptually
novel
single
electron
transfer
strategy
for
C(sp3)–F
activation-enabled
[3
+
2
1]
annulation
of
α-polyfluoromethyl
alkenes
is
developed.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 13, 2025
A
novel
silver-catalyzed
cascade
radical
isonitrile
insertion
and
defluorinative
cyclization
have
been
developed
to
synthesize
CF2H-
phosphinoyl-containing
quinolines
from
ortho-isocyanyl
α-trifluoromethylstyrenes.
The
reaction
proceeded
under
redox-neutral
conditions
allowed
the
construction
of
a
highly
attractive
quinoline
ring
system,
with
simultaneous
formation
CF2H
group
introduction
various
phosphinoyl
groups
in
single
transformation,
showing
operational
simplicity,
wide
substrate
scope,
good
tolerance
for
functional
groups,
remarkable
atom-/stepeconomy.
Mechanistic
studies
indicated
that
is
likely
involve
participation
P-centered
radicals
key
carbanion
intermediates.
Herein,
aromaticity-driven
thio(seleno)ester
group
transfer
from
novel
1,4-dihydropyridine
thio(seleno)esters
to
alkene
feedstocks
is
disclosed
by
merging
palladium
and
photoredox
catalysis.
In
this
process,
photoactivation
of
dihydropyridine
integrated
with
regioselective
hydrometalation
alkenes,
avoiding
photoinduced
Pd-C
bond
homolysis
organopalladium
intermediates.
Additionally,
a
hydroselenocarbonylation
an
accomplished
for
the
first
time
using
bench-stable
selenoester
reagent.
The
activation
mode
thioesters
has
been
illustrated
detailed
mechanistic
studies,
spectroscopic
analysis,
intermediate
trapping,
isotope
labeling
experiments.
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.
