Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(14)
Published: Jan. 5, 2024
Abstract
Mechanochemical
reactions
offer
methodological
and
environmental
advantages
for
chemical
synthesis,
constantly
attracting
attention
within
the
scientific
community.
Besides
unmistakable
sustainability
advantages,
conditions
under
which
mechanochemical
occur,
namely
solventless
conditions,
sometimes
facilitate
isolation
of
otherwise
labile
or
inaccessible
products.
Despite
these
limited
knowledge
exists
regarding
mechanisms
types
intermediates
involved.
Nevertheless,
in
an
expanding
number
cases,
ex
situ
monitoring
techniques
have
allowed
observation,
characterization,
reaction
transformations.
In
this
Minireview,
we
present
a
series
examples
reactive
been
detected
spanning
organic,
organometallic,
inorganic,
materials
chemistry.
Many
were
stabilized
by
non‐covalent
interactions,
played
pivotal
role
guiding
We
believe
that
uncovering
understanding
such
instances,
growing
mechanochemistry
community
could
find
novel
opportunities
catalysis
discover
new
while
achieving
simplification
design.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(42)
Published: Aug. 28, 2023
Abstract
The
combination
of
a
nickel(II)
catalyst
and
mechanoredox
under
ball‐milling
conditions
promotes
mechanical‐force‐driven
C−N
cross‐coupling
reactions.
In
this
nickel(II)/mechanoredox
cocatalyst
system,
the
modulation
oxidation
state
nickel
center,
induced
by
piezoelectricity,
is
used
to
facilitate
highly
efficient
aryl‐amination
reaction,
which
characterized
broad
substrate
scope,
an
inexpensive
catalysts
(NiBr
2
BaTiO
3
),
short
reaction
times,
almost
negligible
quantity
solvents.
Moreover,
can
be
readily
up‐scaled
multi‐gram
scale,
all
synthetic
operations
carried
out
atmospheric
without
need
for
complicated
setups.
Furthermore,
force‐induced
system
suitable
excitation‐energy‐accepting
molecules
poorly
soluble
polyaromatic
substrates
that
are
incompatible
with
solution‐based
nickel(II)/photoredox
cocatalysts.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(65)
Published: July 28, 2023
Here
we
describe
the
development
of
a
sustainable
and
cost-effective
approach
for
catalytic
cross-coupling
reactions
in
mechanochemistry.
It
is
found
that
substrate's
impact
with
vessel
wall
alone
sufficient
to
initiate
reaction,
thus
indicating
milling
balls
function
primarily
as
mixing
agent
direct
mechanocatalytic
Suzuki
coupling.
The
absence
can
be
offset
by
adjusting
rheology
using
liquid-assisted
grinding
(LAG).
LAG
sweet
spot
0.25
μL
mg-1
confirmed
both
resonance
acoustic
mixers
(RAMs)
ball-free
mixer
mills,
higher
than
presence
balls.
RAMs
exhibit
excellent
performance
achieving
yields
90
%
after
60
min
complete
conversion
min.
longevity
significantly
improved
RAM,
allowing
at
least
20
without
deterioration.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(20)
Published: March 4, 2024
Abstract
Birch
reduction
and
similar
dissolved
metal‐type
transformations
hold
significant
importance
in
the
organic
synthesis
toolbox.
Historically,
field
has
been
dominated
by
alkali
metal
reductants.
In
this
study,
we
report
that
largely
neglected,
low‐reactive
alkaline
earth
metals
can
become
powerful
affordable
reductants
when
used
a
ball
mill
under
essentially
solvent‐free
conditions,
presence
of
ethylenediamine
THF
as
liquid
additives.
Calcium
reduce
both
electron‐deficient
electron‐rich
arenes,
with
yields
products
to
those
obtained
lithium
metal.
Magnesium
reveals
enhanced
reducing
power,
enabling
benzoic
acids
while
keeping
aromatic
moieties
intact
allows
for
chemoselective
transformations.
The
developed
mechanochemical
approach
uses
readily
available
safer‐to‐handle
metals,
operates
air
ambient
temperature
be
gram‐scale
preparations.
Finally,
demonstrate
conditions
other
reductive
transformations,
including
amination,
deoxygenation,
dehalogenation,
alkene
alkyne
reductions.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(13), P. 9427 - 9439
Published: June 21, 2024
A
mechanochemical
synthesis
of
1,2-disubstituted
benzimidazoles
from
donor-acceptor
cyclopropyl
ketones
and
1,2-diaminoarenes
under
metal-free
solventless
conditions
is
reported.
The
reaction
does
not
require
inert
promoted
by
a
stoichiometric
amount
1,1,1,3,3,3-hexafluoroisopropanol.
This
cascade
involves
ring-opening,
cyclization,
retro-Mannich
with
aryl
1,2-diamines.
Compared
to
its
solution-phase
counterpart,
this
approach
shows
fast
reactivity
(24
vs
1.5
h).
Mechanistic
investigations
electrospray
ionization
mass
spectrometry
helped
us
propose
the
mechanism.
RSC Mechanochemistry,
Journal Year:
2024,
Volume and Issue:
1(1), P. 38 - 42
Published: Jan. 1, 2024
α-Ketothioamides
are
formed
by
a
mechanochemical
solvent-free
Willgeroth–Kindler-type
reaction
starting
from
acetophenone
derivatives,
amines,
and
elemental
sulfur.
ChemSusChem,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 17, 2025
Solvent-free
techniques
have
gained
considerable
attention
in
recent
years
due
to
their
environmental
advantages
and
potential
enable
chemical
reactivities
beyond
the
reach
of
traditional
solution-based
methods.
Mechanochemistry
has
emerged
as
a
groundbreaking
approach
drive
sustainable
processes.
Despite
its
promise,
some
challenges
still
need
be
explored,
including
overlooked
issue
material
leaching
during
grinding,
phenomenon
which
components
from
milling
media
or
reaction
vessels,
such
stainless
steel,
unintentionally
alter
outcomes.
This
study
investigates
role
metal
reducing
arylnitrosamines
by
using
poorly
soluble
solid
reagent,
thiourea
dioxide
(TDO),
focusing
on
steel
vessels.
By
comparing
conventional
mechanochemical
methods
with
innovative
solvent-free
vibratory
techniques,
we
assess
extent
contamination
impact
efficiency.
These
findings
provide
new
insights
into
how
influences
processes
offer
valuable
guidance
for
optimizing
these
forward-looking
green
methodologies.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(14), P. 8341 - 8347
Published: Jan. 1, 2024
Resonant
Acoustic
Mixing
(RAM)
allows
High
Throughput
Experimentation
(HTE)
using
commercially
available
96-well
plates
as
exemplified
by
the
nickel
catalyzed
C–N
cross
coupling
of
aryl
halides
with
different
amine
and
anilines.
ACS Sustainable Chemistry & Engineering,
Journal Year:
2023,
Volume and Issue:
11(45), P. 16156 - 16164
Published: Oct. 27, 2023
A
solid-state
approach
was
used
to
synthesize
compound
PZ-1190,
a
multitarget
ligand
for
serotonin
and
dopamine
receptors
with
potential
antipsychotic
activity
in
rodents.
Compared
the
classical
batch
synthesis
approach,
developed
multistep
mechanochemical
protocol
improved
overall
yield
(from
32%
56%),
reduced
reaction
time
42
4
h),
decreased
use
of
toxic
reagents
organic
solvents.
All
synthesized
intermediates
PZ-1190
were
isolated
high
purity
by
extraction
without
requirement
chromatographic
purification.
obtained
enantiomeric
(≥99%
ee)
no
impact
grinding
processes
on
integrity
stereocenter.
The
described
procedures
represent
rare
examples
reduction
carboxylic
function,
which
might
open
up
possibility
obtaining
crucial
β-
γ-amino
alcohols
sustainable
manner.
oxidation
an
aliphatic
alcohol
into
aldehyde
using
mechanochemistry
has
also
been
reported
first
time.
results
confirmed
suitability
as
efficient
method
synthesizing
candidates
preclinical
development.
