European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(32)
Published: June 29, 2023
Abstract
De
novo
catalytic
syntheses
of
diarylamines
from
a
palladium‐catalyzed
reductive
Buchwald‐Hartwig
amination
nitroarenes
with
aryl
(pseudo)halides
is
described.
The
exquisite
use
upstream
as
arylamine
surrogates,
the
judicious
selection
bis(pinacolato)diboron
(B
2
pin
)
stoichiometric
reducing
agent,
and
wide
substrate
scope
including
(hetero)aryl
halides
(Cl,
Br
I)
triflates,
constitute
striking
features
current
protocol.
Moreover,
application
this
technique
to
advanced
intermediates
active
pharmaceutical
ingredients
also
proved
successful,
thus
providing
an
alternative
step‐economical
approach
diarylamine‐incorporated
molecules.
Preliminary
mechanistic
investigation
demonstrates
that
amine
nitrosoarene
might
be
involved
in
event.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: May 4, 2022
Abstract
Aromatic
tertiary
amines
are
one
of
the
most
important
classes
organic
compounds
in
chemistry
and
drug
discovery.
It
is
difficult
to
efficiently
construct
from
primary
via
classical
nucleophilic
substitution
due
consecutive
overalkylation.
In
this
paper,
we
have
developed
a
radical
tandem
C-N
coupling
strategy
aromatic
commercially
available
carboxylic
acids
nitroarenes.
A
variety
can
be
furnished
good
yields
(up
98%)
with
excellent
functional
group
compatibility
under
mild
reaction
conditions.
The
use
two
different
also
allows
for
concise
synthesis
nonsymmetric
satisfactory
yields.
Mechanistic
studies
suggest
intermediacy
arylamine–(TPP)Fe(III)
species
might
provide
possible
evidence
an
S
H
2
(bimolecular
homolytic
substitution)
pathway
critical
bond
formation
step.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(10), P. 3552 - 3561
Published: Jan. 1, 2024
A
reductive
and
denitrative
amination
of
nitroarenes
has
been
developed,
allowing
the
highly
selective
synthesis
various
di-
triarylamines.
The
protocol
employed
synthetically
upstream
as
both
electrophiles
amine
sources.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(9), P. 2638 - 2664
Published: Jan. 1, 2024
This
review
describes
the
recent
advances
in
different
reaction
types
and
catalytic
systems
for
construction
of
C–NAr
S–NAr
bonds
by
nitroaromatic
reductive
cross-coupling.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(29), P. 16150 - 16159
Published: July 12, 2023
Palladium-catalyzed
C-N
bond
forming
reactions
are
a
key
tool
in
modern
synthetic
organic
chemistry.
Despite
advances
catalyst
design
enabling
the
use
of
variety
aryl
(pseudo)halides,
necessary
aniline
coupling
partner
is
often
synthesized
discrete
reduction
step
from
nitroarene.
An
ideal
sequence
would
avoid
necessity
this
while
maintaining
reliable
reactivity
palladium
catalysis.
Herein,
we
describe
how
reducing
conditions
enable
new
chemical
steps
and
well-studied
catalysts,
resulting
new,
useful
transformation:
reductive
arylation
nitroarenes
with
chloroarenes
to
form
diarylamines.
Mechanistic
experiments
suggest
that
under
conditions,
BrettPhos-palladium
complexes
catalyze
dual
JACS Au,
Journal Year:
2022,
Volume and Issue:
2(9), P. 2152 - 2161
Published: Aug. 31, 2022
Nitroaromatics
are
tremendously
valuable
organic
compounds
with
a
long
history
of
being
used
as
pharmaceuticals,
agrochemicals,
and
explosives
well
vital
intermediates
to
wide
variety
chemicals.
Consequently,
the
exploration
aromatic
nitration
has
become
an
important
endeavor
in
both
academia
industry.
Herein,
we
report
identification
powerful
nitrating
reagent,
5-methyl-1,3-dinitro-1H-pyrazole,
from
N-nitro-type
reagent
library
constructed
using
practical
N-H
method.
This
behaves
controllable
source
nitronium
ion,
enabling
mild
scalable
broad
range
(hetero)arenes
good
functional
group
tolerance.
Of
note,
our
method
could
be
controlled
by
manipulating
reaction
conditions
furnish
mononitrated
or
dinitrated
product
selectively.
The
value
this
medicinal
chemistry
been
established
its
efficient
late-stage
C-H
complex
biorelevant
molecules.
Density
theory
(DFT)
calculations
preliminary
mechanistic
studies
reveal
that
powerfulness
versatility
due
synergistic
"nitro
effect"
"methyl
effect".
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(41)
Published: Aug. 26, 2023
Nitroaromatic
compounds
represent
one
of
the
essential
classes
molecules
that
are
widely
used
as
feedstock
for
synthesis
intermediates,
preparation
nitro-derived
pharmaceuticals,
agrochemicals,
and
materials
on
both
laboratory
industrial
scales.
We
herein
disclose
efficient,
mild,
catalytic
ipso-nitration
organotrimethylsilanes,
enabled
by
an
electrophilic
N-nitrosaccharin
reagent
allows
chemoselective
nitration
under
mild
reaction
conditions,
while
exhibiting
remarkable
substrate
generality
functional
group
compatibility.
Additionally,
conditions
proved
to
be
orthogonal
other
common
functionalities,
allowing
programming
molecular
complexity
via
successive
transformations
or
late-stage
nitration.
Detailed
mechanistic
investigation
experimental
computational
approaches
strongly
supported
a
classical
aromatic
substitution
(SE
Ar)
mechanism,
which
was
found
proceed
through
highly
ordered
transition
state.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(49), P. 8872 - 8876
Published: Dec. 4, 2023
An
efficient
photocatalytic
C–N
cross-coupling
of
nitroarenes
with
haloarenes
has
been
developed
using
simple
and
cheap
Ni(acac)2
as
a
cocatalyst.
The
reaction
is
confirmed
stepwise
process:
(1)
metal
free
photoinduced
reduction
into
aniline
derivatives
(2)
photo-
Ni-catalyzed
anilines
haloarenes.
conditions
are
mild,
giving
high-value
diarylamines
good
to
excellent
yields
functional
group
tolerance.
