Unraveling aromaticity: the dual worlds of pyrazole, pyrazoline, and 3D carborane
Beilstein Journal of Organic Chemistry,
Год журнала:
2025,
Номер
21, С. 412 - 420
Опубликована: Фев. 21, 2025
A
new
series
of
o
-carborane-fused
pyrazoles
has
been
recently
successfully
synthesized.
This
fusion
was
expected
to
create
a
hybrid
3D/2D
aromatic
system,
combining
the
3D
aromaticity
-carborane
with
2D
pyrazole.
However,
while
boron
cage
retains
its
character,
pyrazole’s
is
lost.
As
result,
rather
than
forming
pyrazoles,
synthesis
yielded
pyrazolines,
which
are
non-aromatic.
The
limited
overlap
between
π
molecular
orbitals
(MOs)
planar
heterocycle
and
n
+
1
MOs
carborane
prevents
significant
electronic
delocalization
two
fused
components.
contrasts
pyrazole
benzene
form
indazole,
where
both
rings
maintain
their
aromaticity.
Our
findings
demonstrate
that
peripheral
σ-aromaticity
π-aromaticity
orthogonal,
making
true
system
unachievable.
highly
aromatic,
generating
negative
NICS
values
(−25
−30
ppm).
We
have
observed
these
high
extend
rings,
leading
incorrect
estimations
Therefore,
relying
solely
on
can
be
misleading,
other
computational
indicators,
along
experimental
or
structural
data,
should
used
accurately
assess
Язык: Английский
Carborane in Polymers—Existent Stipulations and Technological Trademarks
Polymer-Plastics Technology and Materials,
Год журнала:
2025,
Номер
unknown, С. 1 - 27
Опубликована: Фев. 10, 2025
Язык: Английский
Taming Inert B–H Bond with Low Energy Light: A Near-Infrared Light-Induced Approach to Facile Carborane Cluster-Amino Acid Coupling
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 1, 2025
The
selective
functionalization
of
inert
B–H
bonds
in
carborane
clusters
has
been
a
formidable
challenge.
Recent
advances
have
witnessed
such
reactions
through
photoredox
methods
utilizing
ultraviolet
or
visible
light
irradiation.
However,
high-energy
sources
often
suffer
from
poor
energy
efficiency,
limited
substrate
scope,
undesired
side
reactions,
and
low
scalability.
Here,
we
present
the
first
successful
bond
under
low-energy
near-infrared
(NIR)
using
carborane-based
electron
donor–acceptor
complex.
Both
photophysical
investigations
theoretical
modeling
reveal
facile
single-electron
transfer
cage
to
electron-deficient
photocatalyst,
generating
radical
NIR
follow-up
pathway
enables
direct
coupling
carboranes
with
amino
acids
oligopeptides,
yielding
diverse
array
carborane-functionalized
oligopeptides.
Beyond
expanding
known
chemical
space
boron
cluster
derivatives,
further
demonstrate
that
imaging
targeting
capabilities
could
serve
as
promising
multifunctional
carriers
for
neutron
capture
therapy.
Thus,
via
not
only
provides
straightforward
practical
strategy
synthetic
chemistry
but
also
lays
foundation
development
next-generation
boron-containing
biomolecules
advanced
functional
materials.
Язык: Английский
Synthesis of Carboranyl Alkyl Sulfide via Radical Thiol–Ene “Click” Reaction
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 7, 2025
Synthetic
methods
that
feature
mild
reaction
conditions
and
broad
functional
group
tolerance
are
highly
desired
for
the
development
of
third-generation
boron
delivery
agents,
which
significant
neutron
capture
therapy
(BNCT),
a
selective
cancer
treatment
technique.
Molecules
containing
carborane
promising
candidates
as
compounds
BNCT.
Herein,
we
report
an
efficient
radical
thiol-ene
"click"
involving
carboranyl
thiols
unactivated
alkenes
under
photoredox
conditions.
This
affords
moderate
to
excellent
isolated
yields.
The
current
methodology
allows
incorporation
carborane,
valuable
moiety
with
high
content,
into
molecules
outstanding
this
method
makes
it
suitable
late-stage
introduction
bioactive
molecules.
addition
reactivity
thiol
was
investigated
by
DFT
calculations
uncover
impact
3D
aromaticity
on
stabilization
sulfur
centered
radical.
Язык: Английский
Polyoxometalate-Supported Pd(II)-Catalyzed B(9)–H Nitration of o/m-Carboranes
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 7646 - 7652
Опубликована: Апрель 23, 2025
Язык: Английский
A comparative study on nido- and closo-carborane supported zinc-salen catalysts for the ROCOP of epoxides and anhydrides
Dalton Transactions,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Nido
-C
2
B
9
carborane
anion
supported
Zn–salen
complexes
are
superior
to
closo
-carborane
ones
in
ROCOP
of
epoxides
and
anhydrides.
Язык: Английский
Borane-Mediated Polyhedral Expansion to Access Metal-Free Neutral and Cationic Derivatives of closo-Heptaboranes
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 2, 2024
Boranes
with
closed
polyhedral
structures
feature
peculiar
bonding
and
structural
characteristics,
rendering
them
widely
applicable
in
diverse
research
areas
ranging
from
basic
functionalization
reactions
to
applications
such
as
medicine,
nanomaterials,
molecular
electronics,
neutron
capture
therapy.
Among
the
borane
family,
neutral
cationic
heptaborane
B
Язык: Английский
Improved Methods for the Synthesis of B10H14 and N-Heterocycle-Coordinated B9H13 (N-Het·B9H13)
Inorganic Chemistry,
Год журнала:
2024,
Номер
64(1), С. 268 - 274
Опубликована: Дек. 26, 2024
Improved
methods
for
the
synthesis
of
B10H14
and
a
series
N-heterocycle-coordinated
B9H13
complexes
(N-Het·B9H13)
have
been
developed
with
readily
obtained
KB11H14
as
starting
material.
Oxidation
could
provide
in
over
90%
yield.
Then,
N-Het·B9H13
were
prepared
from
as-synthesized
through
situ
multistep
reactions
by
reacting
NaH,
N-heterocycles,
dilute
hydrochloric
acid.
Among
these
complexes,
4-(triphenylvinyl)pyridine-coordinated
(1k)
exhibits
significant
aggregation-induced
emission
(AIE)
effect
THF/H2O
mixed
solution,
8-aminoisoquinoline-coordinated
(2p)
positive
solvatochromism
phenomenon.
These
improved
new
approaches
to
synthesizing
potential
applications
luminescent
materials.
Язык: Английский