ChemSusChem,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 15, 2024
We
report
the
first
metal-
and
catalyst-free
protocol
for
facile
cross-coupling
of
aryl
halides
towards
C-B,
C-P
C-S
bonds
under
solid-state
ball
milling
conditions
via
UV
light
irradiation.
The
reactions
can
be
performed
in
absence
bulk
solvents
at
room
temperature
a
mixer
mill,
yielding
up
to
99
%
being
tolerant
various
functionalized
(X=I
or
Br).
Furthermore,
we
developed
novel
photoreactor
design
increasing
intensity.
With
this
could
demonstrate
that
our
surpasses
classical
solvent
based
as
well
purely
mechanochemical
approaches
terms
green
metrics
energy
efficiency.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 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.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(65)
Published: Aug. 29, 2023
Doping
heteroatoms
into
polycyclic
aromatic
hydrocarbons
(PAHs)
may
alter
their
structures
and
thereby
physical
properties.
This
study
reports
the
construction
of
B/N-codoped
PAHs
via
combining
B-
N-doped
π-systems.
Two
π-extended
were
synthesized
through
Mallory
photoreaction.
Both
feature
a
C48
BN2
π-skeleton,
which
is
assembled
by
linearly
fusing
three
substructures
including
B-doped
sp2
-hybridized
π-moieties
one
pyrene
unit.
In
comparison
to
pristine
analog,
intramolecular
charge
transfer
(ICT)
states
are
distinctly
modulated
fused
π-system
further
incorporated
cyano
group,
leading
tunable
optical
properties,
as
revealed
detailed
theoretical
experimental
analysis.
Furthermore,
these
molecules
have
sufficient
Lewis
acidity
can
coordinate
with
base
form
acid-base
adducts,
notably,
such
intermolecular
complexation
dynamically
modulate
ICT
transitions
photophysical
producing
blue,
green
red
fluorescence.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(48)
Published: Aug. 16, 2024
Abstract
The
rising
prospects
of
mechanochemically
assisted
syntheses
hold
promise
for
both
academia
and
industry,
yet
they
face
challenges
in
understanding
and,
therefore,
anticipating
respective
reaction
kinetics.
Particularly,
dependencies
based
on
variations
milling
equipment
remain
little
understood
globally
overlooked.
This
study
aims
to
address
this
issue
by
identifying
critical
parameters
through
kinematic
models,
facilitating
the
reproducibility
mechanochemical
reactions
across
most
prominent
mills
laboratory
settings,
namely
planetary
mixer
mills.
Through
a
series
selected
experiments
replicating
major
classes
organic,
organometallic,
transition
metal‐catalyzed,
inorganic
from
literature,
we
rationalize
independence
kinetics
when
accumulated
energy
criterion
is
met.
As
step
forward
facilitate
practicability
our
findings,
provide
freely
accessible
online
tool
[†]
that
allows
calculation
different
Our
work
advances
current
mechanochemistry
lays
foundation
future
rational
exploration
rapidly
evolving
field.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(30)
Published: April 29, 2024
Abstract
Die
mechanochemische
Cyclotrimerisierung
von
Nitrilen
ist
ein
einfaches
Synthesekonzept
für
Triazin‐haltige
Moleküle
und
Materialien
adressiert
Probleme
in
Zusammenhang
mit
ungewollter
Karbonisierung
mangelnder
Löslichkeit
verwendeter
Edukte.
In
einer
Festkörperreaktion
der
Kugelmühle
wird
4‐Methylbenzonitril
quantitativ
nur
90
Minuten
zu
Tris(4‐methylphenyl)‐1,3,5‐triazin
umgesetzt.
Ebenso
schnell
das
kovalent‐organische
Triazin‐Netzwerk
CTF‐1
unter
Verwendung
1,4
Dicyanobenzol
aufgebaut.
Das
erhaltene
Material
porös
(650
m
2
g
−1
)
kristallin.
Über
den
mechanischen
Energieeintrag
kann
die
erhaltenen
Konformation
kontrolliert
werden
–
gestaffelten
AB‐Anordnung
überlappenden
AA‐Stapelung.
Weiterhin
über
Variation
Monomere
Vielseitigkeit
dieser
Methode
belegt.
ChemSusChem,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 15, 2024
We
report
the
first
metal-
and
catalyst-free
protocol
for
facile
cross-coupling
of
aryl
halides
towards
C-B,
C-P
C-S
bonds
under
solid-state
ball
milling
conditions
via
UV
light
irradiation.
The
reactions
can
be
performed
in
absence
bulk
solvents
at
room
temperature
a
mixer
mill,
yielding
up
to
99
%
being
tolerant
various
functionalized
(X=I
or
Br).
Furthermore,
we
developed
novel
photoreactor
design
increasing
intensity.
With
this
could
demonstrate
that
our
surpasses
classical
solvent
based
as
well
purely
mechanochemical
approaches
terms
green
metrics
energy
efficiency.
