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.
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 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.
Asian Journal of Organic Chemistry,
Год журнала:
2024,
Номер
13(7)
Опубликована: Май 9, 2024
Abstract
The
excellent
reactivity
of
diaryliodonium
salts
has
primarily
been
attributed
to
the
efficient
departure
iodoarene
unit,
facilitating
a
variety
arylation
reactions.
However,
one
equivalent
as
side‐product
is
chemical
waste
in
these
reactions,
which
was
criticized
by
chemists
for
hindering
its
popularity.
Recently,
development
synthetic
methodology
that
preserve
aryl
iodine
moiety
received
increasing
attention.
Oxidative
rearrangement
reactions
involving
aryliodonium
reagents
have
significantly
addressed
atom‐economic
issue,
thereby
broadening
reaction
scope.
resulting
intricate
aryliodine
products
are
viewed
valuable
synthons
synthesis
natural
products,
pharmaceutical
intermediates
and
other
fine
chemicals.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 15, 2025
A
new
family
of
ortho-hydroxy-substituted
diaryliodonium
salts
was
synthesized
with
1-acetoxy-2-iodobenzenes,
in
which
the
acetyl
group
cleaved
a
one-pot
synthesis.
The
ortho-hydroxyl-substituted
underwent
further
intramolecular
aryl
migration
reaction,
giving
ortho-iodo
diaryl
ethers
either
or
without
presence
bases.
(Vinyl
triflimide)benziodolium
salts
were
developed
as
new
hypervalent
iodine
reagents.
A
cascade
of
diarylation/oxidation
reactions
with
the
benziodolium
was
accomplished
in
presence
palladium
catalysts.
The
reaction
exhibits
extensive
compatibility
readily
available
arylboronic
acids,
giving
a
diverse
array
benzyl
derivatives
good
yields.
benzils
can
serve
versatile
intermediates
fine
chemical
synthesis.
Organic Letters,
Год журнала:
2024,
Номер
26(20), С. 4168 - 4172
Опубликована: Май 10, 2024
By
using
cyclic
(vinyl
triflate)iodonium
salts,
a
novel
triple
Suzuki–Miyaura
reaction
was
accomplished
for
the
synthesis
of
polyaromatic
ethylene
derivatives
in
presence
palladium
catalysts.
The
exhibits
extensive
compatibility
with
wide
range
readily
available
arylboronic
acids,
giving
triaryl-substituted
ethylenes
good
yields.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
366(3), С. 396 - 401
Опубликована: Дек. 9, 2023
Abstract
A
Cu(I)‐catalyzed
synthesis
of
α‐arylated
sulfoxonium
ylides
has
been
achieved
from
mesitylene‐derived
diaryliodonium
salts
and
α‐carbonyl
ylides.
The
reaction
is
believed
to
proceed
via
an
electrophilic
Cu(III)‐aryl
intermediate
that
can
be
trapped
upon
nucleophilic
attack
the
ylide
precursor.
was
tolerant
both
α‐keto
α‐ester‐derived
ylides,
drug‐derived
motifs
electronically‐diverse
arenes,
enabled
direct
32
α‐aryl‐sulfoxonium
in
42–85%
yield.
Rapid Communications in Mass Spectrometry,
Год журнала:
2024,
Номер
38(7)
Опубликована: Фев. 5, 2024
Rationale
Diaryliodonium
salts
are
useful
electrophilic
reagents
in
organic
chemistry,
finding
extensive
applications
arylations
and
photo‐induced
polymerizations.
However,
comprehensive
mechanistic
investigations,
particularly
concerning
the
mass
spectrometric
behaviors
of
diaryliodonium
salts,
relatively
scarce
literature.
Methods
could
be
readily
ionized
using
electrospray
ionization
spectrometry
(ESI‐MS)
to
give
[Ar
1
‐I
+
‐Ar
2
],
high‐resolution
ESI‐tandem
(MS/MS)
experiments
were
conducted
investigate
their
gas‐phase
chemical
reactions.
Results
Investigations
on
ESI‐MS/MS
]
revealed
two
major
fragmentation
patterns:
(1)
reductive
elimination
resulting
diaryl
coupling
product
ion
+•
by
loss
I;
(2)
generation
aryl
cations
or
through
cleavage
C–I
bonds.
We
that
introduction
NO
into
Ar
lead
an
unexpected
O]
MS/MS,
arising
from
O‐atom
transfer
process
.
Particularly,
when
was
ortho
‐positioned
iodine
,
sometimes
exhibited
dominant
behavior.
Conclusions
Comprehensive
studies
theoretical
calculations
provided
strong
support
for
pathway:
‐(
o
‐NO
)]
initially
underwent
a
Smiles
rearrangement
intermediate
‐O‐(
‐NO‐Ar
I)]
which
subsequently
dissociated
[
I]
Herein,
we
proposed
“
effect”
reaction
)],
crucial
determinant
factor
migration
identified
as
reaction.
Abstract
The
transition‐metal‐free
synthesis
of
organic
compounds
especially
heterocycles
is
in
resonance
with
one
the
twelve
principles
proposed
by
Prof.
Paul
Anastas
his
renowned
work
towards
sustainable
development
green
chemistry.
Traditional‐metal‐catalyzed
reactions
often
involve
expensive
or
toxic
metal
catalysts,
and
there
a
growing
interest
developing
more
environmentally
friendly
methods.
arylation
an
important
area
research
chemistry,
particularly
biologically
active
pharmaceuticals.
Arylation
at
different
positions
enhances
potency
stability
pharmaceutically
scaffolds.
In
this
review,
overview
synthetic
protocols
developed
for
variety
heterocyclic
including,
pyrroles,
pyridines,
thiophene,
indole,
oxindoles,
purines,
xanthene,
etc.
has
been
described.
