Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(47)
Опубликована: Сен. 13, 2022
The
inert
milling
balls,
commonly
utilized
in
mechanochemical
reactions,
were
coated
with
a
layer
of
Pd
and
as
catalyst
the
direct
mechanocatalytic
Suzuki
reaction.
With
high
yields
(>80
%),
balls
can
be
recycled
multiple
times
absence
any
solvents,
ligands,
catalyst-molecules
-powders,
while
utilizing
little
0.8
mg
per
ball.
coating
sequence,
support
material,
thickness
examined
towards
archiving
retention,
low
abrasion
conversion.
approach
was
transferred
to
vessels
revealing
interplay
between
catalytically
available
surface
area
mechanical
energy
impact
mechanocatalysis.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(34)
Опубликована: Май 31, 2022
Abstract
The
molecular
Suzuki
cross‐coupling
reaction
was
conducted
mechanochemically,
without
solvents,
ligands,
or
catalyst
powders.
Utilizing
one
catalytically
active
palladium
milling
ball,
products
could
be
formed
in
quantitative
yield
as
little
30
min.
In
contrast
to
previous
reports,
the
adjustment
of
parameters
led
complete
elimination
abrasion
from
thus
enabling
first
reported
systematic
analysis.
XPS,
situ
XRD,
and
reference
experiments
provided
evidence
that
ball
surface
location
catalysis,
allowing
a
mechanism
proposed.
versatility
approach
demonstrated
by
extending
substrate
scope
deactivated
even
sterically
hindered
aryl
iodides
bromides.
Chemical Science,
Год журнала:
2023,
Номер
14(27), С. 7475 - 7481
Опубликована: Янв. 1, 2023
We
demonstrate
the
use
of
a
metal
surface
to
directly
catalyse
copper-catalysed
alkyne-azide
click-coupling
(CuAAC)
reactions
under
conditions
Resonant
Acoustic
Mixing
(RAM)
-
recently
introduced
and
scalable
mechanochemical
methodology
that
uniquely
eliminates
need
for
bulk
solvent,
as
well
milling
media.
By
using
simple
copper
coil
catalyst,
this
work
shows
direct
mechanocatalysis
can
occur
in
an
impact-free
environment,
relying
solely
on
high-speed
mixing
reagents
against
surface,
without
specially
designed
containers
introducing
experimental
setup
enables
real-time
Raman
spectroscopy
monitoring
RAM
processes,
we
0th-order
reaction
kinetics
several
selected
CuAAC
reactions,
supporting
surface-based
catalysis.
The
herein
presented
RAM-based
is
simple,
effective
one-pot,
two-step
synthesis
triazoles
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(27)
Опубликована: Апрель 5, 2023
Abstract
Utilizing
direct
mechanocatalytical
conditions,
the
Sonogashira
coupling
was
successfully
performed
on
surface
of
milling
tools
by
using
pure
Pd
and
coated
steel
balls.
The
optimization
co‐catalyst
forming
additives
led
to
a
protocol,
which
generates
quantitative
yields
under
aerobic
conditions
for
various
substrates
within
as
little
90
minutes.
Using
state‐of‐the‐art
spectroscopic,
diffractive,
well
in
situ
methods
lead
identification
previously
unknown
highly
reactive
complex
copper.
This
new
differs
substantially
from
known
complexes
liquid
phase
couplings,
proving
that
reaction
pathways
mechanochemistry
may
differ
those
established
synthetic
procedures.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(39)
Опубликована: Июль 31, 2023
Abstract
Aryl
fluorides
are
important
structural
motifs
in
many
pharmaceuticals.
Although
the
Balz–Schiemann
reaction
provides
an
entry
to
aryl
from
aryldiazonium
tetrafluoroborates,
it
suffers
drawbacks
such
as
long
time,
high
temperature,
toxic
solvent,
gas
release,
and
low
functional
group
tolerance.
Here,
we
describe
a
general
method
for
synthesis
of
tetrafluoroborates
using
piezoelectric
material
redox
catalyst
under
ball
milling
conditions
presence
Selectfluor.
This
approach
effectively
addresses
aforementioned
limitations.
Furthermore,
can
be
recycled
multiple
times.
Mechanistic
investigations
indicate
that
this
fluorination
may
proceed
via
radical
pathway,
Selectfluor
plays
dual
role
both
source
fluorine
terminal
reductant.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(14), С. 8163 - 8175
Опубликована: Апрель 3, 2023
Cyclodehydrogenation
is
an
essential
synthetic
method
for
the
preparation
of
polycyclic
aromatic
hydrocarbons,
heteroaromatic
compounds,
and
nanographenes.
Among
many
examples,
anionic
cyclodehydrogenation
using
potassium(0)
has
attracted
chemists
because
its
irreplaceable
reactivity
utility
in
obtaining
rylene
structures
from
binaphthyl
derivatives.
However,
existing
methods
are
difficult
to
use
terms
practicality,
pyrophoricity,
lack
scalability
applicability.
Herein,
we
report
development
a
lithium(0)-mediated
mechanochemical
reaction
first
time.
This
could
be
easily
performed
conventional
easy-to-handle
lithium(0)
wire
at
room
temperature,
even
under
air,
1,1′-binaphthyl
complete
within
30
min
afford
perylene
94%
yield.
Using
this
novel
user-friendly
protocol,
investigated
substrate
scope,
mechanism,
gram-scale
synthesis.
As
result,
remarkable
applicability
practicality
over
previous
methods,
as
well
limitations,
were
comprehensively
studied
by
computational
studies
nuclear
magnetic
resonance
analysis.
Furthermore,
demonstrated
two-,
three-,
five-fold
cyclodehydrogenations
synthesis
In
particular,
quinterrylene
([5]rylene
or
pentarylene),
longest
nonsubstituted
molecular
rylene,
was
synthesized
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(28)
Опубликована: Апрель 30, 2024
Abstract
The
development
of
green
and
efficient
deuteration
methods
is
great
significance
for
various
fields
such
as
organic
synthesis,
analytical
chemistry,
medicinal
chemistry.
Herein,
we
have
developed
a
dehalogenative
strategy
using
piezoelectric
materials
catalysts
in
solid‐phase
system
under
ball‐milling
conditions.
This
non‐spontaneous
reaction
induced
by
mechanical
force.
D
2
O
can
serve
both
deuterium
source
an
electron
donor
the
transformation,
eliminating
need
additional
stoichiometric
exogenous
reductants.
A
series
(hetero)aryl
iodides
be
transformed
into
deuterated
products
with
high
incorporation.
method
not
only
effectively
overcomes
existing
synthetic
challenges
but
also
used
labelling
drug
molecules
derivatives.
Bioactivity
experiments
molecule
suggest
that
D‐ipriflavone
enhances
inhibitory
effects
on
osteoclast
differentiation
BMDMs
vitro
.
ACS Organic & Inorganic Au,
Год журнала:
2024,
Номер
4(5), С. 432 - 470
Опубликована: Авг. 7, 2024
In
recent
years,
mechanochemistry
has
become
an
innovative
and
sustainable
alternative
to
traditional
solvent-based
synthesis.
Mechanochemistry
rapidly
expanded
across
a
wide
range
of
chemistry
fields,
including
diverse
organic
compounds
active
pharmaceutical
ingredients,
coordination
compounds,
organometallic
complexes,
main
group
frameworks,
technologically
relevant
materials.
This
Review
aims
highlight
advancements
accomplishments
in
mechanochemistry,
underscoring
its
potential
as
viable
eco-friendly
conventional
solution-based
methods
the
field
synthetic
chemistry.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(65)
Опубликована: Июль 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.
