While
photocatalysts
are
generally
responsible
for
radical
generation
from
bench
stable
diaryliodonium
salts,
recent
reports
have
emerged
exhibiting
photocatalyst-free
using
select
Lewis
bases
as
activators.
Herein,
we
demonstrate
1)
the
ability
of
numerous
to
enable
light-driven
and
2)
these
radicals
can
be
captured
by
transition-metals
coupling
reactions.
These
results
first
step
toward
developing
new
organometallic
aryl
reactions
without
photocatalysts.
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:
2023,
Volume and Issue:
25(43), P. 7900 - 7905
Published: Oct. 26, 2023
We
report
an
organophotoredox-catalyzed
stereoselective
allylic
arylation
of
MBH
acetates
with
a
palette
diaryliodonium
triflates
(DAIRs)
to
provide
the
corresponding
trisubstituted
alkenes
in
moderate
good
yields.
The
method
could
be
extended
three-component
coupling
involving
1,4-diazabicyclo[2.2.2]octane
bis(sulfur
dioxide)
adduct
(DABSO)
as
sulfur
dioxide
surrogate
for
synthesis
biologically
relevant
sulfones.
Both
these
reactions
were
carried
out
under
mild
conditions
featuring
broad
scope,
robustness,
and
appreciable
functional
group
tolerance.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(11)
Published: Jan. 15, 2024
Abstract
Visible‐light‐activated
organic
reactions
unlock
novel
avenues
for
complex
molecular
transformations,
impossible
under
standard
“thermal”
conditions,
which
makes
them
powerful
tools
in
the
arsenal
of
synthetic
chemistry.
However,
transition
metal‐based
or
photoredox
catalysts
are
often
used
to
ensure
productive
absorption
visible
light,
might
be
not
desirable
medicinal
chemistry
and
industry
due
toxicity,
low
sustainability,
high
cost
most
photocatalysts.
A
more
environmentally
economically
benign
approach
is
based
on
formation
transient
electron
donor‐acceptor
(EDA)
complexes
between
two
reagents
a
reagent
an
additive,
that
readily
absorb
acting
as
internal
photosensitizers.
Within
EDA
complex‐based
arylation
strategies,
chemical
transformations
mediated
by
noncovalent
interaction
molecules,
namely
electron‐poor
aryl
halides
their
equivalents
electron‐rich
nucleophilic
additives.
Moreover,
besides
stoichiometric
organocatalysis
can
achieved
certain
cases
through
regeneration
donor
molecules
course
reaction.
Photoexcitation
induces
single
transfer
(SET)
process
generate
radical
species
step.
This
Review
will
focus
state‐of‐the‐art
strategies
utilizing
halides,
aryldiazonium,
diaryliodonium,
arylsulfonium
arylphosphonium
salts
reactants,
published
mainly
last
five
years.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
27(4), P. 1012 - 1017
Published: Jan. 21, 2025
Vicinal
bis(tetraarylphosphonium)
salts
have
scarcely
been
reported
in
the
literature.
In
this
study,
we
demonstrate
that
visible-light-induced
difunctionalization
of
ortho-trifluoromethylsulfonylated
diaryliodonium
conveniently
furnishes
bis(phosphonium)
without
additional
catalysts
or
photoinitiators.
The
methodology
establishes
a
practical
platform
for
preparation
using
readily
available
tertiary
phosphines.
are
anticipated
to
garner
great
deal
interest
catalytic
and
medicinal
chemistry.
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.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(14), P. 9923 - 9928
Published: July 1, 2024
Diethyl
acetamidomalonate
(DEAM)
has
been
widely
used
for
the
synthesis
of
α-amino
acids
via
C-alkylation
under
basic
conditions
followed
by
hydrolysis/decarboxylation.
In
contrast,
C-arylation
this
reagent
remains
undeveloped.
Herein,
we
report
a
novel
strategy
racemic
α-arylglycines
based
on
selective
arylation
DEAM
with
diaryliodonium
salts
mild,
transition
metal-free
conditions.
The
reaction
features
good
functional
group
tolerance
and
easy
scalability
is
applicable
to
chemoselective
C-H-modification
arenes
including
approved
drugs,
thus
enabling
straightforward
approach
complex
that
would
be
challenging
make
otherwise.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(61)
Published: Aug. 26, 2024
In
recent
times,
diaryliodonium
reagents
(DAIRs)
have
witnessed
a
resurgence
as
arylating
reagents,
especially
under
photoinduced
conditions.
However,
reactions
proceeding
through
electron
donor-acceptor
(EDA)
complex
formation
with
DAIRs
are
restricted
to
electron-rich
reacting
partners
serving
donors
due
the
well-known
cage
effect.
We
discovered
practical
and
high-yielding
visible-light-induced
EDA
platform
generate
aryl
radicals
from
corresponding
use
them
synthesize
key
chalcogenides.
this
process,
an
array
of
dichalcogenides
react
in
presence
1,4
diazabicyclo[2.2.2]octane
(DABCO)
cheap
readily
available
donor,
furnishing
variety
di(hetero)aryl
aryl/alkyl
chalcogenides
good
yields.
The
method
is
scalable,
features
broad
scope
yields,
operates
open-to-air
chalcogenation
technology
suitable
for
late-stage
functionalizations
disulfide
bioconjugations
facilitates
access
biologically
relevant
thioesters,
dithiocarbamates,
sulfoximines,
sulfones.
Moreover,
applies
synthesizing
diverse
pharmaceuticals,
such
vortioxetine,
promazine,
mequitazine,
dapsone,
amenable
Beilstein Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
20, P. 2891 - 2920
Published: Nov. 13, 2024
Diaryliodonium
salts
have
become
widely
recognized
as
arylating
agents
in
the
last
two
decades.
Both,
symmetrical
and
unsymmetrical
forms
of
these
serve
effective
electrophilic
reagents
various
organic
syntheses.
The
use
diaryliodoniums
C–C
carbon–heteroatom
bond
formations,
particularly
under
metal-free
conditions,
has
further
enhanced
popularity
reagents.
In
this
review,
we
concentrate
on
arylation
reactions
involving
carbon
other
heteroatoms,
encompassing
rearrangement
absence
any
metal
catalyst,
summarize
advancements
made
five
years.
Herein,
we
demonstrate
1)
that
Lewis
base
heteroatom
coordination
to
diaryliodonium
salts
is
not
required
for
light-driven
radical
generation
and
2)
radicals
generated
by
this
route
can
be
captured
transition-metals
coupling
reactions.
These
results
are
the
first
step
toward
developing
new
aryl
reactions
without
exogenous
photocatalysts.
We
demonstrate
1)
that
halogen
bonding
is
not
critical
for
enabling
light-driven
radical
generation
from
diaryliodonium
salts
and
2)
radi-cals
generated
by
this
route
can
be
captured
transition-metals
C–H
arylation
reactions.
These
results
are
the
first
step
toward
devel-oping
new
metal-catalyzed
aryl
couplings
without
exogenous
photocatalysts.
