Abstract
This
review
provides
an
overview
on
recent
progress
in
mechanochemical
transition
metal
catalyzed
C─H
functionalization.
Solventless
operation
and
enhanced
reaction
efficiency
makes
synthesis
a
more
sustainable
alternative
to
conventional
approaches.
By
including
comparison
between
methods
solvent‐based
protocols,
this
chemists
with
valuable
insights
into
the
relative
sustainability
of
these
solventless
strategies.
enables
informed
decision‐making
when
selecting
for
functionalization
based
specific
needs.
Moreover,
identifies
existing
gaps
discusses
necessary
steps
establish
it
as
mainstream
approach.
bridging
gaps,
can
further
enhance
utility
adoption
methodologies,
contributing
practices
synthetic
chemistry.
Chemical Reviews,
Год журнала:
2022,
Номер
122(24), С. 17479 - 17646
Опубликована: Окт. 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,
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.
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
.
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(15), С. 2462 - 2478
Опубликована: Июнь 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,
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.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(47)
Опубликована: Июнь 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
Organic Process Research & Development,
Год журнала:
2023,
Номер
27(2), С. 269 - 275
Опубликована: Фев. 3, 2023
Chemical
reactions
that
take
place
in
a
ball
mill
and
the
absence
of
bulk
reaction
solvent
present
different
safety
profiles
to
stirred
solution
reactions.
Herein,
we
describe
steps
researcher
may
better
ensure
they
have
considered
some
hazards
measures
emerge
minimize
risk
themselves
their
colleagues.
CCS Chemistry,
Год журнала:
2023,
Номер
5(8), С. 1737 - 1744
Опубликована: Май 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
Green Chemistry,
Год журнала:
2024,
Номер
26(14), С. 8341 - 8347
Опубликована: Янв. 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.
