Organic & Biomolecular Chemistry,
Journal Year:
2023,
Volume and Issue:
21(11), P. 2440 - 2446
Published: Jan. 1, 2023
A
novel
approach
for
the
production
of
halogen
cations
through
reaction
halogens
with
silver
ions
is
described
in
this
paper.
On
basis,
regioselective
synthesis
3-haloquinolines
and
3-halospirocyclohexadienones
realized
solvent
regulation.
The
gram-scale
compatibility
complex
substrates
demonstrate
synthetic
potential
protocol,
which
will
be
an
appealing
strategy
organic
synthesis.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(14), P. 9755 - 9767
Published: March 26, 2024
Hydroxylated
(hetero)arenes
are
valued
in
many
industries
as
both
key
constituents
of
end
products
and
diversifiable
synthetic
building
blocks.
Accordingly,
the
development
reactions
that
complement
address
limitations
existing
methods
for
introduction
aromatic
hydroxyl
groups
is
an
important
goal.
To
this
end,
we
apply
base-catalyzed
halogen
transfer
(X-transfer)
to
enable
direct
C–H
hydroxylation
mildly
acidic
N-heteroarenes
benzenes.
This
protocol
employs
alkoxide
base
catalyze
X-transfer
from
sacrificial
2-halothiophene
oxidants
aryl
substrates,
forming
SNAr-active
intermediates
undergo
nucleophilic
hydroxylation.
Key
process
use
2-phenylethanol
inexpensive
hydroxide
surrogate
that,
after
substitution
rapid
elimination,
provides
hydroxylated
arene
styrene
byproduct.
Use
simple
2-halothiophenes
allows
6-membered
1,3-azole
derivatives,
while
a
rationally
designed
2-halobenzothiophene
oxidant
extends
scope
electron-deficient
benzene
substrates.
Mechanistic
studies
indicate
reversible,
suggesting
deprotonation,
halogenation,
steps
operate
synergy,
manifesting
unique
selectivity
trends
not
necessarily
dependent
on
most
position.
The
utility
method
further
demonstrated
through
streamlined
target
molecule
syntheses,
examples
regioselectivity
contrast
alternative
methods,
scalable
recycling
thiophene
oxidants.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(8), P. 1580 - 1601
Published: Jan. 1, 2024
Considering
the
wide
occurrence
and
extensive
application
of
organic
chlorides
in
many
research
fields,
development
easy,
practical
green
chlorination
methodologies
is
much
needed.
In
oxidative
strategy,
active
chlorinating
species
can
be
RSC Advances,
Journal Year:
2025,
Volume and Issue:
15(11), P. 8750 - 8756
Published: Jan. 1, 2025
An
efficient
and
convenient
protocol
for
copper-promoted
oxidative
mono-
di-bromination
of
8-aminoquinoline
amides
using
hydrogen
bromide
(HBr)
as
the
brominating
reagent
dimethyl
sulfoxide
(DMSO)
a
mild
oxidant
has
been
developed.
Green Chemistry,
Journal Year:
2025,
Volume and Issue:
27(8), P. 2197 - 2202
Published: Jan. 1, 2025
We
present
the
first
catalyst-free
fluorination
of
unactivated
tertiary
alkyl
halides
via
ball
milling.
This
method
offers
short
reaction
times,
minimal
solvent
usage,
and
is
applicable
to
synthesis
key
intermediates
for
ledipasvir.
RSC Advances,
Journal Year:
2025,
Volume and Issue:
15(11), P. 8523 - 8528
Published: Jan. 1, 2025
A
simple,
efficient
and
environmentally
friendly
methodology
for
the
halodecarboxylation
of
anisole
analogues
using
Fe(NO3)3·9H2O/KBr
or
NaI
at
room
temperature
was
developed.
In
this
method,
most
substrates
with
an
electron-donating
group
afforded
corresponding
products
in
good
to
excellent
yields,
whereas
those
electron-withdrawing
low
moderate
yields.
More
importantly,
protocol
also
applicable
gram-scale
synthesis.
It
is
hoped
that
will
be
highly
useful
organic
Chemistry - An Asian Journal,
Journal Year:
2023,
Volume and Issue:
18(19)
Published: Aug. 21, 2023
Abstract
This
report
describes
the
synthesis
of
a
new
NNSe
pincer
ligand
and
its
mono‐
dinuclear
palladium(II)
complexes.
In
absence
base,
palladium
complex
(
C1
)
was
isolated,
while
in
presence
Et
3
N
base
mononuclear
C2
obtained.
The
complexes
were
characterized
using
techniques
like
1
H,
13
C{
H}
nuclear
magnetic
resonance
(NMR),
fourier
transform
infrared
(FTIR),
high‐resolution
mass
spectrometry
(HRMS),
ultraviolet‐visible
(UV‐Visible),
cyclic
voltammetry.
Both
showed
coordination
mode
with
distorted
square
planar
geometry.
has
two
ligands
attached
through
Pd−Pd
bond
fashion.
air
moisture‐insensitive,
thermally
robust
used
as
catalyst
for
decarboxylative
direct
C−H
heteroarylation
(hetero)arenes.
Among
complexes,
better
catalytic
activity.
A
variety
(hetero)arenes
successfully
activated
(43–87
%
yield)
only
2.5
mol
loading
under
mild
reaction
conditions.
PPh
Hg
poisoning
experiments
suggested
homogeneous
nature
catalysis.
plausible
pathway
proposed
catalyzed
activation
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(7), P. 1575 - 1582
Published: Jan. 16, 2024
Abstract
A
nitrosonium
catalyzed
bromination
of
electron‐rich
arenes
has
been
developed,
using
bromide
salts
as
bromine
sources,
oxygen
gas
a
terminal
oxidant
and
Brønsted
acids
(sulfuric
acid,
TFA
or
HBr).
This
arene
process
is
free
transition
metals,
proceeding
in
acetic
acid
under
mild
temperatures
(25–50
°C)
to
give
brominated
with
good
excellent
yields.
Our
mechanistic
studies
indicated
that
this
oxidative
reaction
by
nitrosnium
ion
(NO
+
),
without
the
involvement
Br
2
.
The
kinetic
isotope
effect
was
measured
pentadeuteriophenyl
phenyl
ether
(
k
H
/
D
=1.1).
Green Synthesis and Catalysis,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
A
visible-light-induced
brominated
spirocyclization
of
N-arylpropiolamides
and
CBr4
for
the
synthesis
3-bromo-azaspiro[4,5]trienones
is
reported
here.
This
process
allows
formation
C-Br,
C-C,
C=O
bonds
in
a
single
reaction
via
cascade
radical
addition/ipso-cyclization/oxidative
dearomatization
sequence.
protocol
also
features
high
functional
group
tolerance,
operational
simplicity
use
molecular
oxygen
as
an
oxidant
well
sustainable
photocatalyst-
additive-free
conditions
at
room
temperature.
Meanwhile,
presented
straightforward
strategy
has
been
applied
to
several
biologically
active
compounds.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(22), P. 16809 - 16827
Published: Nov. 1, 2024
A
photocatalytic
three-component
cascade
reaction
of
readily
available
enaminones,
hydrazines,
and
CBr4
for
the
synthesis
bromo-substituted
pyrazoles
in
one
pot
has
been
demonstrated.
This
strategy
involves
intermolecular
C-N/C-Br
bond
formation
represents
an
efficient
approach
to
construction
4-bromo-substituted
with
high
regioselectivity,
broad
substrate
scope,
good
functional
group
tolerance,
convenient
operation,
mild
conditions.
Mechanistic
investigations
show
that
this
proceeds
via
cyclization
enaminones
followed
by
a
regioselective
bromination
using
as
"Br"
source.
Journal of Chemical Crystallography,
Journal Year:
2024,
Volume and Issue:
54(4), P. 336 - 346
Published: Aug. 19, 2024
Abstract
Crystals
of
mono-
and
dibromo
as
well
two
isomeric
tribromocymantrenes
[Mn(C
5
H
5-n
Br
n
)(CO)
2
(PPh
3
)]
(n
=
1–3)
were
obtained
examined
by
X-ray
diffraction.
The
degree
substitution
has
only
minor
influence
on
bond
lengths
angles.
However,
the
relative
orientations
bromo
substituents
PPh
ligand
orientation
cyclopentadienyl
ring
MnC
P
tripod
are
sensitive
to
number
position
bromines.
All
compounds
show
weak
Br…O
interactions,
mostly
combined
with
hydrogen
bonds,
while
Br…Br
interactions
unimportant.
These
lead
sometimes
complicated
chain
structures.
Graphical
In
crystal
structures
bromocymantrenes
3)
]
a
combination
bonds
Br…O/Br…Br
leads
one-dimensional
molecular
chains
or
double-chains,
which
not
further
connected
in
other
dimensions.
