YAKUGAKU ZASSHI,
Год журнала:
2023,
Номер
144(1), С. 7 - 14
Опубликована: Дек. 31, 2023
Decarboxylative
arylation
of
α,α-difluoro-β-ketoacid
salts
with
diaryliodonium(III)
has
been
developed
to
synthesize
α-aryl-α,α-difluoromethyl
ketones,
which
are
attractive
synthetic
intermediates
for
various
difluorobenzyl
units.
This
additive-free
represents
an
alternative
approach
conventional
methods
that
rely
on
transition
metal
catalysts
and/or
organometallic
compounds.
The
reaction
involves
sequential
ligand
exchange
difluoroketoacid
tosylate
diaryliodonium
salt,
followed
by
decarboxylative
coupling.
Various
functional
groups,
including
ester,
nitro,
cyano,
heteroarenes,
and
aryl
halide
were
tolerated
during
the
present
reaction.
resulting
ketones
can
be
transformed
into
corresponding
esters,
amides,
difluoromethyl
compounds,
commonly
found
in
biologically
active
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.
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.
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.
ACS Omega,
Год журнала:
2024,
Номер
9(24), С. 26275 - 26284
Опубликована: Июнь 5, 2024
Yb(OTf)3
promoted
the
Krapcho
decarboxylation
of
2,2-difluoro-3-oxopropanoate,
and
a
subsequent
aldol
reaction
was
achieved.
This
process
is
first
example
generating
difluoroenolates
through
decarboxylation-type
process,
large
number
carbonyl
compounds
are
applicable
to
reaction.
The
protocol
complete
one-pot
that
uses
bench-stable
nonhygroscopic
2,2-difluoro-3-oxopropanoate
generate
difluoroenolate.
strategy
has
been
applied
for
synthesis
CF2-containing
bioactive
GABAB
agonists,
contributing
drug
design.
Acyloxyphosphonium
ions
readily
and
conveniently
prepared
in-situ
from
parent
a,a-difluorinated
carboxylic
acids
commodity
chemicals
are
established
as
convenient
acyl
electrophiles
that
to
be
used
in
a
copper-catalyzed
cross-coupling
protocol
with
organozinc
reagents
carbon
nucleophiles
smoothly
afford
a,a-difluoroketones.
Several
can
employed
efficiently
using
this
protocol.
In
the
case
of
CF2H-
CF3-ketones
di-
trifluoroacetic
acid
under
copper-free
conditions.
The
transformations
proceed
mild
reaction
conditions
(0
oC-RT),
produce
target
compounds
short
times
(45
min)
exhibit
good
chemoselectivity
functional
group
compatibility.
Notably,
methodology
was
also
demonstrated
effective
for
synthesis
non-fluorinated
ketones
(benzophenones)
directly
benzoic
acids.
RSC Sustainability,
Год журнала:
2024,
Номер
2(9), С. 2626 - 2631
Опубликована: Янв. 1, 2024
A
sustainable
and
catalyst-free
strategy
has
been
developed
for
the
synthesis
of
propargylamines
by
a
three-component
doubly
decarboxylative
coupling
reaction.
