Angewandte Chemie,
Год журнала:
2024,
Номер
136(14)
Опубликована: Янв. 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,
Год журнала:
2024,
Номер
63(14)
Опубликована: Янв. 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,
Год журнала:
2024,
Номер
63(48)
Опубликована: Авг. 16, 2024
Abstract
The
rising
prospects
of
mechanochemically
assisted
syntheses
hold
promise
for
both
academia
and
industry,
yet
they
face
challenges
in
understanding
and,
therefore,
anticipating
respective
reaction
kinetics.
Particularly,
dependencies
based
on
variations
milling
equipment
remain
little
understood
globally
overlooked.
This
study
aims
to
address
this
issue
by
identifying
critical
parameters
through
kinematic
models,
facilitating
the
reproducibility
mechanochemical
reactions
across
most
prominent
mills
laboratory
settings,
namely
planetary
mixer
mills.
Through
a
series
selected
experiments
replicating
major
classes
organic,
organometallic,
transition
metal‐catalyzed,
inorganic
from
literature,
we
rationalize
independence
kinetics
when
accumulated
energy
criterion
is
met.
As
step
forward
facilitate
practicability
our
findings,
provide
freely
accessible
online
tool
[†]
that
allows
calculation
different
Our
work
advances
current
mechanochemistry
lays
foundation
future
rational
exploration
rapidly
evolving
field.
Cell Reports Physical Science,
Год журнала:
2024,
Номер
5(2), С. 101831 - 101831
Опубликована: Фев. 1, 2024
Nickel-catalyzed
radical
relayed
dicarbofunctionalizations
of
olefins,
utilizing
carbon
electrophiles
as
coupling
partners,
present
a
powerful
strategy
for
the
streamlined
construction
aliphatic
structures.
However,
traditional
solution-phase
methods
encounter
challenges
such
need
bulk
solvents,
limited
long
reaction
times,
and
air-/moisture-sensitive
reagents.
As
an
alternative
strategy,
ball-mill-enabled
metal-catalyzed
cross-coupling
reactions
have
gained
attention
due
to
their
high
reactivity
atomic
efficiency.
While
many
are
single-
two-component
methodologies,
three-component
solid-state
remain
relatively
scarce.
In
this
work,
we
report
first,
our
knowledge,
ball-milling-enabled
Ni-catalyzed
reductive
dicarbofunctionalization
alkenes.
Two
distinct
readily
available
electrophiles,
Csp2
Csp3
halides,
simultaneously
installed
across
variety
olefins
at
room
temperature
in
highly
regioselective
manner
withing
1.5
h.
By
harnessing
benefits
ball
milling
reactions,
anticipate
further
advancements
sustainable
efficient
synthetic
methodologies.
Green Energy & Environment,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 1, 2024
Traditional
chemical
processes
often
generate
substantial
waste,
leading
to
significant
pollution
of
water,
air,
and
soil.
Developing
eco-friendly
methods
is
crucial
for
economic
environmental
sustainability.
Mechano-driven
chemistry,
with
its
potential
material
recyclability
minimal
byproducts,
well-aligned
green
chemistry
principles.
Despite
origins
over
2000
years
ago
nearly
200
scientific
investigation,
mechano-driven
has
not
been
widely
implemented
in
practice.
This
likely
due
a
lack
comprehensive
understanding
the
complex
physical
effects
mechanical
forces,
which
challenge
reaction
efficiency
scalability.
review
summarizes
historical
development
discusses
progress
across
various
mechanisms,
including
mechanochemistry,
tribochemistry,
piezochemistry,
contact
electrification
(CE)
chemistry.
CE-induced
reactions,
involving
ion
transfer,
electron
radical
generation,
are
detailed,
emphasizing
dominant
role
radicals
initiated
by
transfer
influence
through
electrical
double
layer
(EDL)
formation.
Advancing
efficient,
eco-friendly,
controllable
technologies
can
reduce
reliance
on
traditional
energy
sources
(such
as
electricity
heat)
toxic
reagents,
fostering
innovation
synthesis,
catalytic
technologies,
establishing
new
paradigm
broader
applications.
To
address
the
growing
demand
for
more
sustainable
and
greener
chemistry,
mechanochemical
methodologies
are
emerging
as
key
players.
However,
to
date
there
has
been
little
data
highlighting
benefits
of
these
rising
technologies
with
regard
process
scale-up
activities
or
implementation
in
commercial
production
scale.
Herein,
we
report
first
application
bead-mill
technology
(Dyno®-mill)
synthesis
Acetaminophen,
known
under
brand
name
Paracetamol.
Using
Beckmann
rearrangement,
optimized
solvent-free
methodology
delivered
a
final
product
on
scale
several
tens
grams.
In
comparison
current
solvent-based
process,
proposed
achieves
higher
yield
while
also
allowing
removal
solvents
chemical
reaction,
hereby
reducing
one
extensive
drivers
waste
generation.
The
approach
was
compared
using
combination
green
metrics
EcoScale
score.
paracetamol
scores
highest
all
over
currently
used
solution-based
processes.
Catalysis Communications,
Год журнала:
2024,
Номер
186, С. 106831 - 106831
Опубликована: Янв. 1, 2024
This
work
describes
a
simple
method
for
the
preparation
of
5-hydroxymethylfurfural
(HMF)
by
dehydrating
fructose
in
DMSO,
either
with
use
an
affordable
catalyst
or
catalyst-free
manner.
process
can
be
accompanied,
under
harsh
conditions,
bromide-catalyzed
Kornblum
oxidation
hydroxyl
group
solvent,
resulting
formation
2,5-diformylfuran
(DFF).
The
optimized
techniques
presented
this
study
serve
as
foundation
production
valuable
biobased
furanic
platform
chemicals
from
renewable
sources
any
laboratory,
stimulating
development
sustainable
chemistry
and
research
related
fields
worldwide.
Abstract
A
general
and
modular
protocol
is
reported
for
olefin
difunctionalization
through
mechanochemistry,
facilitated
by
cooperative
radical
ligand
transfer
(RLT)
electron
catalysis.
Utilizing
mechanochemical
force
catalytic
amounts
of
2,2,6,6‐tetramethylpiperidinyloxyl
(TEMPO),
ferric
nitrate
can
leverage
nitryl
radicals,
nitrooxy‐functional
group
via
RLT,
mediate
an
catalysis
cycle
under
room
temperature.
diverse
range
activated
unactivated
alkenes
exhibited
chemo‐
regioselective
1,2‐nitronitrooxylation
solvent‐free
or
solvent‐less
conditions,
showcasing
excellent
functional
tolerance.
Mechanistic
studies
indicated
a
significant
impact
mechanochemistry
highlighted
the
nature
this
nitrative
process.
