Abstract
A
mechanochemical,
highly
regioselective
rhodium(III)‐catalyzed
C─H
methylation
of
8‐methylquinolines
is
reported.
The
method
reported
in
this
study,
often
solvent‐free
or
uses
minimal
solvent
(liquid
assisted
grinding),
operates
without
external
heating
under
mild
reaction
conditions,
demonstrating
tolerance
for
various
functional
groups.
Moreover,
the
time
significantly
reduced
compared
to
solvent‐based
variant.
Notably,
can
be
carried
out
using
a
pestle
and
mortar
instead
ball
milling
as
well,
highlighting
operational
simplicity
approach
achieving
challenging
C(sp
3
)‐H
activation
more
sustainable
conditions.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Май 27, 2024
Nitroxides
find
application
in
various
areas
of
chemistry,
and
a
more
in-depth
understanding
factors
controlling
their
reactivity
with
metal
complexes
is
warranted
to
promote
further
developments.
Here,
we
report
on
the
effect
centre
Lewis
acidity
both
distribution
O-
N-centered
spin
density
2,2,6,6-tetramethylpiperidine-N-oxyl
(TEMPO)
turning
TEMPO
from
N-radical
mode
scavenger
metal-TEMPO
systems.
We
use
Et(Cl)Zn/TEMPO
model
reaction
system
tuneable
solid
state
solution.
Among
products,
unique
acid-base
adduct
Cl
ACS Catalysis,
Год журнала:
2024,
Номер
unknown, С. 13747 - 13758
Опубликована: Авг. 30, 2024
With
the
growing
emphasis
on
cost-
and
atom-economical
chemical
synthesis,
mechanochemistry
has
attracted
considerable
attention
for
providing
environmentally
friendly
alternatives
to
traditional
solvent-based
organic
transformations.
Herein,
we
demonstrate
use
of
facilitate
alkene
dihalogenation
via
iron-mediated
radical
ligand
transfer
(RLT)
catalysis,
producing
diverse
vicinal
dichloro,
dibromo,
bromochloro
molecules.
The
method
is
characterized
by
its
simplicity,
rapid
reaction
time,
high
chemo-
regioselectivity,
broad
functional
group
tolerance,
accommodating
both
activated
unactivated
alkenes
alkynes.
Mechanistic
insights
suggest
nature
these
processes,
underscoring
effectiveness
mechanochemically
driven
RLT
catalysis
modular
functionalization
unsaturated
hydrocarbons.
Chemical Communications,
Год журнала:
2024,
Номер
60(77), С. 10629 - 10641
Опубликована: Янв. 1, 2024
Large
or
repeated
mechanical
loads
degrade
polymeric
materials
by
accelerating
chain
fragmentation.
This
mechanochemical
backbone
fracture
usually
occurs
homolysis
of
otherwise
inert
C-C,
C-O
and
C-S
bonds,
generating
highly
reactive
macroradicals.
Because
is
detrimental
on
its
own
the
resulting
macroradicals
can
initiate
damaging
reaction
cascades,
a
major
thrust
in
contemporary
polymer
mechanochemistry
to
suppress
it,
release
"hidden
length"
that
dissipates
local
molecular
strain.
Here
we
summarize
an
emerging
complementary
strategy
channelling
mechanochemically
generated
cascades
form
new
load-bearing
chemical
which
enables
self-healing
self-strengthening,
and/or
generate
mechanofluorescence,
could
yield
detailed
quantitative
understanding
how
material-failure-inducing
macroscopic
distribute
across
network.
We
aim
identify
generalizable
lessons
derivable
from
reported
implementations
this
outline
key
challenges
adapting
it
diverse
loading
scenarios.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 9, 2024
Abstract
Starting
from
N
‐acyl
sulfonimidamides,
mechanochemically
generated
rhodium
nitrenoids
undergo
intramolecular
N−O
couplings
to
provide
unprecedented
1,3,2,4‐oxathiadiazole
3‐oxides
in
good
excellent
yields.
The
cyclization
proceeds
efficiently
with
a
catalyst
loading
of
only
0.5
mol
%
the
presence
phenyliodine(III)
diacetate
(PIDA)
as
oxidant.
Neither
an
inert
atmosphere
nor
additional
heating
is
required
this
solvent‐free
procedure.
Under
heat
or
blue
light,
newly
formed
five‐membered
heterocycles
function
nitrene
precursors
reacting
sulfoxides
exemplified
by
imidation
dimethyl
sulfoxide.
Abstract
Mechanochemical
reactions
by
ball
milling
have
opened
new
avenues
in
chemical
synthesis.
Particularly,
mechanochemistry
has
facilitated
the
reaction
of
insoluble
materials
to
simplify
stablished
synthetic
protocols
and
develop
ones.
One
notable
application
involves
use
calcium
carbide
(CaC
2
)
as
a
C
‐synthon
through
mechanochemistry,
which
offered
more
practical
alternative
incorporate
‐units
compared
conventional
highly
flammable
gaseous
acetylene.
For
example,
milling,
acetylenic
anions
[C
]
2−
found
CaC
been
harnessed
for
synthesis
diverse
functional
carbon
well
discrete
organic
molecules.
This
Concept
aims
contribute
conceptualization
this
innovative
approach
while
highlighting
both
its
advantages
challenges
inherent
.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 22, 2024
Abstract
Organic
synthesis
has
historically
relied
on
solution‐phase,
polar
transformations
to
forge
new
bonds.
However,
this
paradigm
is
evolving,
propelled
by
the
rapid
evolution
of
radical
chemistry.
Additionally,
organic
witnessing
a
simultaneous
resurgence
in
mechanochemistry,
formation
bonds
solid‐state,
further
contributing
shift
status
quo.
The
aforementioned
advances
chemistry
have
predominantly
occurred
solution
phase,
while
majority
mechanochemical
feature
transformations.
Herein,
we
discuss
rapidly
advancing
area
synthesis:
reactions.
Solid‐state
reactions
offer
improved
green
metrics,
better
reaction
outcomes,
and
access
intermediates
products
that
are
difficult
or
impossible
reach
solution.
This
review
explores
these
context
small
molecule
synthesis,
from
early
findings
current
state‐of‐the‐art,
underscoring
pivotal
role
solid‐state
likely
play
sustainable
chemical
synthesis.
Inorganic Chemistry,
Год журнала:
2024,
Номер
63(32), С. 15247 - 15258
Опубликована: Июль 29, 2024
Group
1
metal
molecular
chemistry
is
dominated
by
a
+1
oxidation
state,
while
0
state
widespread
in
the
metals.
A
more
exotic,
yet
still
available,
of
group
-1,
i.e.,
alkalide.
Reported
as
early
1970s,
alkalides
appear
every
modern
inorganic
textbook
an
iconic
chemical
curiosity,
their
reactivity
remains
unexplored.
This
due
to
synthetic
hurdles.
In
this
work,
we
report
first
facile
synthesis
archetypical
alkalide
complex,
[Na
ACS Sustainable Chemistry & Engineering,
Год журнала:
2024,
Номер
12(37), С. 13774 - 13782
Опубликована: Сен. 3, 2024
(S)-aromatic
epoxides
are
of
great
importance
in
the
production
pharmaceuticals
and
biologically
active
natural
products.
Consequently,
developing
efficient,
ecofriendly,
economical
methods
for
continues
to
be
tremendous
interest
organic
synthesis.
Herein,
we
report
a
novel
protocol
efficient
synthesis
by
coupling
mechanochemical
biocatalysis
from
commercially
available
cheap
materials.
The
first
step
process
is
halogenation
aromatic
ketones
with
N-halosuccinimides
(NXS)
under
ball-milling
conditions
form
α-haloaromatic
ketones.
This
followed
one-pot
asymmetric
bioreduction–cyclization
sequence
affording
various
good
yields,
which
pure
enough
without
further
purification.
Compared
traditional
chemical
approaches,
this
mechano-biocatalytic
has
prominent
advantages,
including
inexpensive
starting
materials,
short
reaction
time,
simplicity
operation,
environmental
benignity,
broad
substrate
spectrum,
excellent
enantioselectivities,
easy
isolation
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 9, 2024
Abstract
Starting
from
N
‐acyl
sulfonimidamides,
mechanochemically
generated
rhodium
nitrenoids
undergo
intramolecular
N−O
couplings
to
provide
unprecedented
1,3,2,4‐oxathiadiazole
3‐oxides
in
good
excellent
yields.
The
cyclization
proceeds
efficiently
with
a
catalyst
loading
of
only
0.5
mol
%
the
presence
phenyliodine(III)
diacetate
(PIDA)
as
oxidant.
Neither
an
inert
atmosphere
nor
additional
heating
is
required
this
solvent‐free
procedure.
Under
heat
or
blue
light,
newly
formed
five‐membered
heterocycles
function
nitrene
precursors
reacting
sulfoxides
exemplified
by
imidation
dimethyl
sulfoxide.
