Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(28), С. 15118 - 15127
Опубликована: Июль 10, 2023
Precise
control
in
reaction
selectivity
is
the
goal
modern
organic
synthesis,
and
it
has
been
widely
studied
throughout
synthetic
community.
In
comparison,
of
divergent
reactivity
a
given
reagent
under
different
conditions
relatively
less
explored
aspect
chemical
selectivity.
We
herein
report
an
unusual
between
polycyclic
aromatic
hydrocarbons
periodic
acid
H5IO6
(1),
where
product
outcome
dictated
by
choice
conditions.
That
is,
reactions
solution-based
condition
give
preferentially
C-H
iodination
products,
while
solvent-free
mechanochemical
provide
oxidation
quinone
products.
Control
experiments
further
indicated
that
not
intermediate
toward
vice
versa.
Mechanistic
studies
unveiled
situ
crystalline-to-crystalline
phase
change
2
during
ball-milling
treatment,
we
assigned
as
polymeric
hydrogen-bond
network
1.
believe
this
crystalline
shields
more
embedded
electrophilic
I═O
group
1
from
bias
pathway
(with
I═O)
solid
state.
Collectively,
work
demonstrates
mechanochemistry
can
be
employed
to
completely
switch
unmask
hidden
reagents.
Mechanochemical
transformations
have
made
chemists
enter
unknown
territories,
forcing
a
different
chemistry
perspective.
While
questioning
or
revisiting
familiar
concepts
belonging
to
solution
chemistry,
mechanochemistry
has
broken
new
ground,
especially
in
the
panorama
of
organic
synthesis.
Not
only
does
it
foster
"thinking
outside
box",
but
also
opened
reaction
paths,
allowing
overcome
weaknesses
traditional
exactly
where
use
well-established
solution-based
methodologies
rules
out
progress.
In
this
Review,
reader
is
introduced
an
intriguing
research
subject
not
yet
fully
explored
and
waiting
for
improved
understanding.
Indeed,
study
mainly
focused
on
that,
although
impossible
solution,
become
possible
under
mechanochemical
processing
conditions,
simultaneously
entailing
innovation
expanding
chemical
space.
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(19), С. 6680 - 6714
Опубликована: Янв. 1, 2023
The
quantitative
assessment
of
the
greenness
mechanochemical
processes
for
green
metrics
were
calculated
is
herein
reported.
A
general
introduction
to
topic,
variables
influencing
reaction
outcome
and,
an
outlook
are
also
provided.
Synthesis,
Год журнала:
2023,
Номер
55(16), С. 2439 - 2459
Опубликована: Май 3, 2023
Abstract
Although
known
for
millennia,
it
is
only
recently
that
mechanochemistry
has
received
serious
attention
by
chemists.
Indeed,
during
the
past
15
years
an
extraordinary
number
of
reports
concerning
solid-state
chemical
transformations
through
grinding
and
milling
techniques
have
been
recorded.
This
short
review
discusses
circumstances
led
this
renaissance,
highlighting
present
intense
interest
in
so-called
green
chemistry,
enabling
capacity
to
handle
insoluble
substrates,
identification
profound
influence
additives
can
on
mechanochemically
activated
reactions.
The
core
account
focuses
salient
developments
synthetic
organic
especially
amino
acid
peptide
mechanosynthesis,
successful
employment
mechanochemical
activation
combination
with
asymmetric
organocatalysis,
promising
enzymatic
whole
cell
biocatalysis,
remarkable
achievement
multicomponent
selective
reactions
via
complex,
multistep
reaction
pathways,
mechanosynthesis
representative
heterocycles.
final
section
comments
some
pending
tasks
area,
such
as
scaling-up
processes
be
practical
use
industry,
requirement
easier
more
efficient
control
parameters
monitoring
devices,
consequently
careful
analysis
additional
procedures
a
proper
understanding
phenomena.
1
Introduction
2
Brief
History
Mechanochemistry
3
Milling
Equipment
Reaction
Parameters
4
Attributes
That
Propelled
Its
Present
Renaissance
4.1
Enormous
Attention
Being
Presently
Paid
Sustainable
Chemistry
4.2
Reduced
Energy
Consumption
4.3
Additive-Based
4.4
Handling
Insoluble
Reactants
4.5
‘Impossible’
Reactions
Are
Successful
4.6
Air-
Water-Sensitive
Reagents
Ball
5
Salient
Developments
Mechanochemical
Activation
Synthetic
Organic
5.1
Amino
Acid
Peptide
Mechanosynthesis
5.2
Asymmetric
Synthesis
Organocatalysis
under
Ball-Milling
Conditions
5.3
Mechanoenzymology
5.4
Multicomponent
Activated
5.5
Heterocycles
Modification
6
Future
Directions
6.1
Scaling-Up
Protocols
6.2
Temperature-Controlled
6.3
Understanding
Transformations
6.4
Emerging
Techniques
7
Conclusions
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(44)
Опубликована: Апрель 28, 2023
Mechanochemistry
provides
an
environmentally
benign
platform
to
develop
more
sustainable
chemical
processes
by
limiting
raw
materials,
energy
use,
and
waste
generation
while
using
physically
smaller
equipment.
A
continuously
growing
research
community
has
steadily
showcased
examples
of
beneficial
mechanochemistry
applications
at
both
the
laboratory
preparative
scale.
In
contrast
solution-based
chemistry,
mechanochemical
have
not
yet
been
standardized,
thus
scaling
up
is
still
a
nascent
discipline.
The
purpose
this
Minireview
highlight
similarities,
differences
challenges
various
approaches
that
successfully
applied
for
range
scales.
We
hope
provide
discussion
starting
point
those
interested
in
further
developing
commercial
use
and/or
industrialisation.
Industrial & Engineering Chemistry Research,
Год журнала:
2023,
Номер
62(27), С. 10487 - 10497
Опубликована: Июнь 27, 2023
Herein,
we
described
a
cost-effective,
viable
methodology
for
using
an
iron-based
industrial
waste
material
known
as
iron
oxide
dust
(IOD),
also
Hematite
(α-Fe2O3)
the
synthesis
of
their
chemically
reduced
magnetic
version
named
r-IOD
(Fe3O4@α-Fe2O3).
showed
its
visible-light-promoted
photoresponsive
behavior
photodegradation
higher
concentration
(∼1000
mg
L–1)
five
different
model
dyes
(methyl
orange
(MO),
metanil
yellow
(MY),
Congo
red
(CR),
methylene
blue
(MB),
crystal
violet
(CV),
and
mixtures)
in
presence
sunlight.
Based
on
kinetic
radical
trapping
experiments,
mechanistic
analysis
supports
significant
involvement
superoxide
radicals
responsible
photodegradation.
Moreover,
soil
samples
were
externally
spiked
with
further
analyzed
similar
set
experiments
to
support
viability
reported
procedure,
concerning
utilization
materials.
Langmuir,
Год журнала:
2023,
Номер
39(36), С. 12865 - 12877
Опубликована: Авг. 28, 2023
The
MoS2-based
reduced
graphene
oxide
aerogel
(MoS2-rGOA)-assisted
organic
transformation
reactions
are
presented.
MoS2-rGOA
is
used
as
a
heterogeneous
catalyst
for
the
reduction
of
benzene
derivatives
such
benzaldehyde,
nitrobenzene,
and
benzonitrile
to
benzyl
alcohol,
aniline,
benzamide
their
derivatives,
respectively,
in
green
solvents
(water/methanol)
reducing
agents
(hydrazine
hydrate
having
N2
H2
byproducts).
mechanistic
features
pathway,
substrate
scope,
best
suitable
conditions
by
varying
temperature,
solvent,
agent,
loading,
time,
etc.
optimized.
All
synthesized
products
obtained
quantitative
yield
with
purity
well
characterized
based
on
nuclear
magnetic
resonance
analysis.
Further,
it
also
observed
that
our
efficiently
recyclable
works
checked
up
5
cycles.
Organic Process Research & Development,
Год журнала:
2024,
Номер
28(4), С. 816 - 830
Опубликована: Март 14, 2024
From
the
context
of
sustainability,
contemporary
synthetic
organic
chemistry
practices
require
significant
transformation,
as
indicated
by
various
sustainability
matrices
like
atom
economy,
process
mass
intensity
(PMI),
E-factor,
and
DOZN.
These
factors
have
evidently
unveiled
inherent
inefficiencies
intrinsic
to
conventional
protocols
identified
solvents
principal
causative
agent.
In
response,
utilization
water
a
primary
reaction
medium
for
transformations
has
emerged
an
appealing
alternative.
This
approach
flourished
with
emergence
micellar
catalysis,
where
amphiphilic
molecules
alter
bulk
aqueous
medium's
solvation
properties
promote
desired
chemical
transformation
under
milder
sustainable
conditions.
After
2010,
this
technology
gained
considerable
momentum
established
foundational
framework
performing
reactions
conditions,
consequently
mitigating
dependency
on
hazardous
solvents.
perspective,
recent
advances
in
field
catalysis
will
be
discussed
industrial
applications,
along
future
directions
challenges
associated
regime.
Industrial & Engineering Chemistry Research,
Год журнала:
2023,
Номер
62(23), С. 9091 - 9103
Опубликована: Июнь 1, 2023
Here,
we
describe
a
simpler-sustainable
approach
for
fabricating
photo-active
magnetite
nanoparticles
(Fe3O4-NPs)
using
an
almost
inert
waste
material
known
as
red-colored
iron
oxide
dust
(IOD).
The
synthesized
heterogeneous
catalyst
Fe3O4-NPs
showed
photoactivity
in
the
presence
of
sunlight
and
was
used
photodegradation
higher
concentration
(∼1000
mg
L–1)
noxious
nitrophenols
their
mixtures
aqueous
medium.
Kinetic
studies,
including
control
tests,
have
been
performed
to
compare
photocatalytic
performance
vs
IOD
artificial
bulb
light.
half-life
percentage
strongly
suggest
that
influences
faster
rate
mixtures.
Radical
trapping
experiments
were
identify
reactive
active
species
responsible
photodegradation,
results
support
significant
involvement
hydroxyl
radicals
along
with
holes.
Further,
real-life
assessment
photocatalyst
explored
by
checking
its
capability
industrial
wastewater
soil
samples
via
external
spiking
nitrophenols.
Moreover,
are
compared
two
commercially
available
Fe3O4,
which
comparable
results,
case
trinitrophenol
(TNP)
mixture,
slightly
better
results.
quantitative
studies
green
chemistry
metrics
DOZN
software-based
calculations
supported
greener
more
sustainable
process
present
method
synthesis
Fe3O4-NPs.
Advanced Materials,
Год журнала:
2023,
Номер
35(52)
Опубликована: Июль 5, 2023
In
recent
years
it
is
shown
that
mechanochemical
strategies
can
be
beneficial
in
directed
conversions
of
organic
compounds.
Finding
new
reactions
proved
difficult,
and
due
to
the
lack
mechanistic
understanding
reaction
events,
respective
efforts
have
mostly
remained
empirical.
Spectroscopic
techniques
are
crucial
shedding
light
on
these
questions.
this
overview,
opportunities
challenges
solid-state
nuclear
magnetic
resonance
(NMR)
spectroscopy
field
mechanochemistry
discussed.
After
a
brief
discussion
basics
high-resolution
NMR
under
magic-angle
spinning
(MAS)
conditions,
seven
for
presented,
ranging
from
ex
situ
approaches
structurally
elucidated
products
obtained
by
milling
potential
limitations
approaches.
Particular
strengths
NMR,
instance
differentiating
polymorphs,
NMR-crystallographic
structure-determination
protocols,
or
detecting
weak
noncovalent
interactions
molecular-recognition
events
employing
proton-detected
experiments
at
fast
MAS
frequencies,