Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
31(8)
Published: Oct. 27, 2024
Abstract
Aryl‐chlorides
and
‐fluorides
are
common
building
blocks,
but
their
use
in
synthesis
is
limited
by
the
high
stability
of
Ar−X
bonds.
The
generation
aryl
radicals
via
activation
strong
bonds
possible
through
irradiation
tailor‐made
organic
anions,
which
become
reductants
stronger
than
lithium
metal.
We
report
that
combination
visible
light
with
cheap
diphenylacetic
acid
dianion
an
even
better
tool,
showing
excellent
activity
across
a
variety
complex
substrates
providing
opportunities
for
late‐stage
drug
modification.
chemoselectively
activated
presence
more
easily
reducible
functions,
such
as
Alk‐Cl
ones
carbonyl
groups.
These
results
pave
way
to
original
synthetic
strategies
would
be
otherwise
considered
impossible.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(46), P. 8290 - 8295
Published: Nov. 14, 2023
We
report
a
photoredox
system
comprising
sodium
iodide,
triphenyl
phosphine,
and
N,N,N',N'-tetramethylethylenediamine
(TMEDA)
that
can
form
self-assembled
tetrameric
electron
donor-acceptor
(EDA)
complex
with
diaryliodonium
reagents
(DAIRs)
furnish
aryl
radicals
upon
visible
light
irradiation.
This
practical
mode
of
activation
DAIRs
enables
arylation
an
array
heterocycles
under
mild
conditions
to
provide
the
respective
heteroaryl-(hetero)aryl
assembly
in
moderate
excellent
yields.
Detailed
mechanistic
investigations
photophysical
DFT
studies
provided
insight
into
reaction
mechanism.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(9), P. 1975 - 1979
Published: Feb. 27, 2024
We
report
the
use
of
simple
1,4-dihydropyridine
anions
as
a
general
platform
for
promoting
single-electron
photoreductions.
In
presence
mild
base,
1,4-dihydropyridines
were
shown
to
effectively
promote
hydrodechlorination
and
borylation
aryl
chlorides
photodetosylation
N-tosyl
aromatic
amines
under
visible
light
irradiation.
Our
studies
also
demonstrate
that
C4
substituent
can
influence
reactivity
these
anions,
reducing
unwanted
side
reactions
like
hydrogen
atom
transfer
back-electron
transfer.
Chemical Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 7, 2025
Constructing
chemical
bonds
under
green
sustainable
conditions
has
drawn
attention
from
environmental
and
economic
perspectives.
The
dissociation
of
(hetero)aryl-halide
is
a
crucial
step
most
arylations
affording
(hetero)arene
derivatives.
Herein,
we
summarize
the
(hetero)aryl
halides
activation
enabling
direct
(hetero)arylation
trapping
reagents
construction
highly
functionalized
(hetero)arenes
benign
conditions.
strategies
for
aryl
iodides
are
classified
into
(a)
hypervalent
iodoarene
followed
by
functionalization
thermal/photochemical
conditions,
(b)
aryl-I
bond
in
presence
bases
with/without
organic
catalysts
promoters,
(c)
photoinduced
presence/absence
organophotocatalysts,
(d)
electrochemical
direct/indirect
electrolysis
mediated
organocatalysts
mediators
acting
as
electron
shuttles,
(e)
electrophotochemical
redox-active
organocatalysts.
These
modes
result
exhibiting
diverse
reactivity
formal
cations/radicals/anions
aryne
precursors.
coupling
these
reactive
intermediates
with
leads
to
facile
selective
formation
C-C
C-heteroatom
bonds.
ecofriendly,
inexpensive,
functional
group-tolerant
offer
alternatives
transition
metal-based
catalysis.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 1, 2025
Aryl
chlorides
are
more
commercially
available
and
lower
cost
compared
with
aryl
bromides
iodides.
However,
the
use
of
(hetero)aryl
as
radical
precursors
for
di(hetero)arylation
alkenes
remains
an
underdeveloped
area.
Furthermore,
existing
examples
theses
reactions
predominantly
confined
to
activated
alkenes.
In
this
study,
we
introduce
a
photoirradiation-promoted
benzophenone-catalyzed
1,2-di(hetero)arylation
process
that
is
applicable
both
unactivated
alkenes,
utilizing
cyanoarenes
sources.
Importantly,
method
allows
simultaneous
introduction
two
heterocycles
high
regioselectivity.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(17), P. 12591 - 12609
Published: Aug. 14, 2024
The
incorporation
of
gem-difluoromethylene
units
into
organic
molecules
remains
a
formidable
challenge.
Conventional
methodologies
for
constructing
aryldifluoromethyl
derivatives
relied
on
the
use
high-functional
fluorinating
regents
under
harsh
conditions.
Herein,
we
report
general
and
efficient
photoredox
catalytic
systems
defluoroalkylation
readily
available
trifluoromethylarenes
through
selective
C–F
cleavage
to
deliver
gem-difluoromethyl
radicals
which
proceed
reductive
addition
both
electron-donating
withdrawing
alkenes
transition-metal
free
Mechanistic
studies
reveal
that
thiol
serves
as
photocatalyst
HAT
reagent
visible
light
irradiation.
This
synergistic
photocatalysis
catalysis
protocol
exhibits
ample
salient
features
such
high
chemo-
regioselectivity,
broad
substrate
scope,
amenable
gram-scale
synthesis
late-stage
modification
bioactive
molecules.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
unknown
Published: May 18, 2024
Abstract
α‐Aryl
cyclocarbonyls
are
important
building
blocks
in
organic
synthesis.
While
many
methods
have
been
developed
for
their
synthesis,
the
use
of
readily
available
and
inexpensive
aryl
chlorides
as
arylating
reagent
remains
rare.
Herein,
we
report
an
α‐arylation
cyclic
ketones
with
under
reductive
electrophotocatalytic
conditions.
2,6‐Diisopropylphenyl‐containing
naphthalenemonoimide
was
identified
optimal
electrophotocatalyst,
allowing
electron‐deficient
well
electron‐rich
mild
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(20), P. 15164 - 15169
Published: Oct. 7, 2024
An
I2-mediated
annulation
of
3-aminopyrazoles
with
indole-3-carboxaldehydes
has
been
demonstrated
for
the
first
time.
This
tandem
strategy
allows
facile
construction
indole-pyrimidine-pyrazole-fused
tetracyclic
heteroarenes
that
are
otherwise
inaccessible
by
existing
methods.
These
fused
heterocycles
exhibited
enhanced
antifungal
activities
against
Valsa
mali
and
Botryosphaeria
dothidea
compared
commercial
Xemium
fungicide.
