Chemistry - Methods,
Journal Year:
2022,
Volume and Issue:
2(12)
Published: July 12, 2022
Abstract
Catalyzed
reactions
of
organic
substrates
that
operate
continuously
by
extrusion
techniques
are
rare.
In
this
study,
we
developed
a
mechanochemical
bromination
unactivated
naphthalene
(
1
)
with
1,3‐dibromo‐5,5‐dimethylhydantoin
DBDMH
),
catalyzed
zeolites
in
ball
mill.
The
use
enabled
the
atom
economy
reaction
to
be
superior
compared
other
brominating
agents
evaluated.
Among
tested,
FAU‐type
zeolite
demonstrated
high
catalytic
activity
and
recyclability.
success
route
on
small
scale
development
continuous
twin‐screw
extrusion.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(24), P. 17479 - 17646
Published: Oct. 14, 2022
Alkenes
and
their
derivatives
are
featured
widely
in
a
variety
of
natural
products,
pharmaceuticals,
advanced
materials.
Significant
efforts
have
been
made
toward
the
development
new
practical
methods
to
access
this
important
class
compounds
by
selectively
activating
alkenyl
C(sp2)–H
bonds
recent
years.
In
comprehensive
review,
we
describe
state-of-the-art
strategies
for
direct
functionalization
sp2
C–H
C–F
until
June
2022.
Moreover,
metal-free,
photoredox,
electrochemical
also
covered.
For
clarity,
review
has
divided
into
two
parts;
first
part
focuses
on
currently
available
using
different
alkene
as
starting
materials,
second
describes
bond
easily
accessible
gem-difluoroalkenes
material.
This
includes
scope,
limitations,
mechanistic
studies,
stereoselective
control
(using
directing
groups
well
metal-migration
strategies),
applications
complex
molecule
synthesis
where
appropriate.
Overall,
aims
document
considerable
advancements,
current
status,
emerging
work
critically
summarizing
contributions
researchers
working
fascinating
area
is
expected
stimulate
novel,
innovative,
broadly
applicable
functionalizations
coming
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(39)
Published: July 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.
Advanced Synthesis & Catalysis,
Journal Year:
2022,
Volume and Issue:
364(15), P. 2462 - 2478
Published: June 16, 2022
Abstract
Cross
dehydrogenative
coupling
(CDC)
reactions
have
become
a
convenient
synthetic
strategy
for
the
synthesis
of
various
(het)aromatic
scaffolds.
In
recent
times
ball
milling
has
emerged
as
powerful
tool
to
perform
in
greener
way.
The
current
review
highlights
applications
cross
under
towards
useful
molecules
more
efficient
and
manner.
magnified
image
Cell Reports Physical Science,
Journal Year:
2024,
Volume and Issue:
5(2), P. 101831 - 101831
Published: Feb. 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.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(28)
Published: April 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
.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(47)
Published: June 18, 2024
Mechanochemical
reactions,
achieved
through
milling,
grinding,
or
other
mechanical
actions,
have
emerged
as
a
solvent-free
alternative
to
traditional
solution-based
chemistry.
Mechanochemistry
not
only
provides
the
opportunity
eliminate
bulk
solvent
use,
reducing
waste
generation,
but
also
unveils
new
reaction
strategy
which
enables
realization
of
reactions
previously
inaccessible
in
solution.
While
majority
organic
facilitated
by
force
traditionally
follow
two-electron
transfer
pathways
similar
their
counterparts,
field
mechanochemically
induced
single-electron
(SET)
has
witnessed
rapid
development.
This
review
outlines
examples
mechanochemical
SET
process,
focusing
on
reagents
that
initiate
SET,
thereby
positioning
mechanochemistry
burgeoning
within
realm
Advanced Science,
Journal Year:
2024,
Volume and Issue:
11(33)
Published: July 3, 2024
α-halo
alkylboronic
esters,
acting
as
ambiphilic
synthons,
play
a
pivotal
role
versatile
intermediates
in
fields
like
pharmaceutical
science
and
organic
chemistry.
The
sequential
transformation
of
carbon-boron
carbon-halogen
bonds
into
broad
range
carbon-X
allows
for
programmable
bond
formation,
facilitating
the
incorporation
multiple
substituents
at
single
position
streamlining
synthesis
complex
molecules.
Nevertheless,
synthetic
potential
these
compounds
is
constrained
by
limited
reaction
patterns.
Additionally,
conventional
methods
often
necessitate
use
bulk
toxic
solvents,
exhibit
sensitivity
to
air/moisture,
rely
on
expensive
metal
catalysts,
involve
extended
times.
In
this
report,
ball
milling
technique
introduced
that
overcomes
limitations,
enabling
external
catalyst-free
multicomponent
coupling
aryl
diazonium
salts,
alkenes,
simple
halides.
This
approach
offers
general
straightforward
method
obtaining
diverse
array
thereby
paving
way
extensive
utilization
synthons
fine
chemicals.
CCS Chemistry,
Journal Year:
2023,
Volume and Issue:
5(8), P. 1737 - 1744
Published: May 8, 2023
Difluoromethyl
ethers
are
formed
through
mechanochemical
reactions
of
alcohols
with
difluorocarbene
in
a
mixer
mill.The
protocol
could
be
applied
to
primary,
secondary,
and
tertiary
alcohols,
yielding
the
corresponding
products
excellent
yields
(up
99%)
after
1
h
reaction
time
at
room
temperature.The
transformations
proceeded
under
solvent-free
conditions,
followed
by
product
purification
filtration,
which
drastically
reduced
amount
waste
generated
during
process.CsCl
+
TMSCF
2
Br
Solvent-free
Pure
filtration
rt,
1°,
2°,
3°alcohols
Mild
conditions
Operationally
simple
Difluorocarbene
pathway
RSC Mechanochemistry,
Journal Year:
2024,
Volume and Issue:
1(2), P. 189 - 195
Published: Jan. 1, 2024
The
mechanochemical
protecting-group-free
amidation
of
hydroxycarboxylic
acids
is
presented.
transformation
applied
to
the
synthesis
imatinib
via
a
two-fold
C–N
bond
construction
sequence
that
bypasses
chlorinated
genotoxic
intermediate.
