Abstract
A
transition
metal-free
strategy
is
reported
for
the
site-selective
O-arylation
of
cyclic
1,3-dicarbonyls
with
polyfluoroarenes.
This
method
offers
a
straightforward
and
alternative
pathway
synthesis
aryl
ethers,
accommodating
wide
array
functional
groups.
Furthermore,
practical
value
this
methodology
underscored
by
its
facile
scalability
to
gram-level
reactions,
potential
diverse
synthetic
applications,
aptitude
complex
molecules
modifications.
Chemical Communications,
Год журнала:
2024,
Номер
60(76), С. 10552 - 10555
Опубликована: Янв. 1, 2024
We
report
boron-intermediary
ligand
transfer
of
diaryliodonium
salt,
synthesizing
polyfluorolalkyl
aryl
ethers
in
the
absence
transition
metal
catalyst
or
base.
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 2927 - 2938
Опубликована: Фев. 4, 2025
Cyclic
aryliodoniums
are
widely
used
as
arylative
reagents
via
a
ring
opening
process.
Despite
the
numerous
synthetic
achievements,
precise
control
of
regioselective
unsymmetrical
cyclic
remains
fundamental
challenge
in
chemistry.
Herein,
we
report
an
effective
substrate
and
catalyst
cocontrolled
chemoselective
reclosing
with
alkynes.
Particularly,
ortho-installed
aryliodonium
amido
groups
palladium
catalysts
direct
switch
formation
either
C–N
or
C–O
bond
during
annulation.
The
experiment
density
functional
theory
(DFT)
study
indicate
cooperative
mode
influenced
by
steric
electronic
effects
substrates
catalysts.
This
method
features
broad
scope,
good
compatibility,
high
chemoselectivity,
providing
divergent
tetra-heterocyclic
arenes.
It
further
demonstrated
practicality
this
protocol
complex
derived
from
series
clinical
drugs
efficiency.
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.
Beilstein Journal of Organic Chemistry,
Год журнала:
2024,
Номер
20, С. 1020 - 1028
Опубликована: Май 3, 2024
Diaryliodonium(III)
salts
are
versatile
reagents
that
exhibit
a
range
of
reactions,
both
in
the
presence
and
absence
metal
catalysts.
In
this
study,
we
developed
efficient
synthetic
methods
for
preparation
aryl(TMP)iodonium(III)
carboxylates,
by
reaction
(diacetoxyiodo)arenes
or
iodosoarenes
with
1,3,5-trimethoxybenzene
diverse
organocarboxylic
acids.
These
reactions
were
conducted
under
mild
conditions
using
trimethoxyphenyl
(TMP)
group
as
an
auxiliary,
without
need
additives,
excess
reagents,
counterion
exchange
further
steps.
protocols
compatible
wide
substituents
on
(hetero)aryl
iodine(III)
compounds,
including
electron-rich,
electron-poor,
sterically
congested,
acid-labile
groups,
well
broad
aliphatic
aromatic
carboxylic
acids
synthesis
carboxylates
high
yields.
This
method
allows
hybridization
complex
bioactive
fluorescent-labeled
diaryliodonium(III)
salts.
Organic Letters,
Год журнала:
2024,
Номер
26(25), С. 5347 - 5352
Опубликована: Июнь 17, 2024
α-Fluorinated
aryl
esters
pose
a
challenge
in
synthesis
via
O-arylation
of
α-fluorinated
carboxylates
owing
to
their
low
reactivities.
This
limitation
has
been
addressed
by
combining
silver
catalyst
with
aryl(trimethoxyphenyl)iodonium
tosylates
access
esters.
We
envision
that
the
catalytic
system
involves
high-valent
species
generated
oxidation
silver(I)
salt.
The
present
method
provided
synthetic
protocol
for
various
including
fluorinated
analogs
drug
derivatives.
Beilstein Journal of Organic Chemistry,
Год журнала:
2024,
Номер
20, С. 2891 - 2920
Опубликована: Ноя. 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.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(5), С. 2926 - 2938
Опубликована: Фев. 14, 2024
We
have
developed
a
highly
efficient
base-
and
additive-free
chemoselective
CuO-catalyzed
strategy
for
the
O-arylation
of
2-oxindoles
to
synthesize
2-phenoxy-3H-indole
2-phenoxy-1H-indole
derivatives
in
presence
diaryl
iodonium
salts.
This
method
offers
variety
O-arylated
oxindoles
good
excellent
yields
under
relatively
milder
reaction
conditions.
Furthermore,
this
methodology
was
extended
2-pyridinone
isoindoline-1-one
as
well.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 14, 2024
Abstract
An
efficient
organoiodine‐catalysed
intramolecular
direct
C−N
bond
oxidative
coupling
reaction
is
presented.
Structurally
diverse
3‐(mono)substituted
oxindoles
were
rapidly
obtained
in
a
complex
system
up
to
87
%
yield.
Various
N
‐alkoxy‐2‐phenylpropanamides
well‐tolerated.
This
study
showed
that
the
electronic
effects
on
aromatic
ring
of
reactants
have
crucial
effect
selectivity
(C−N/C−O)
cyclisation
products.
In
addition,
gram‐scale
synthesis
and
late‐stage
modification
oxindole
derivatives
revealed
practical
application
this
transformation.
Chemical Communications,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 31, 2024
This
study
reports
the
chemoselective
arylocyclizations
utilizing
two
distinct
types
of
hypervalent
iodine
reagents,
resulting
in
synthesis
dibenzoxazepinones
under
transition-metal-free
conditions.
