Cooperative Anion−π Catalysis with Chiral Molecular Cages toward Enantioselective Desymmetrization of Anhydrides
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 10, 2025
Exploiting
novel
noncovalent
interactions
for
catalysis
design
represents
a
fascinating
direction.
For
the
flexible
and
relatively
weak
anion−π
interactions,
manipulation
of
two
or
more
π-acidic
surfaces
cooperative
activation
is
highly
desirable.
Here,
we
demonstrate
strategy
based
on
chiral
molecular
cages
with
V-shaped
electron-deficient
cavities
synergic
binding
dicarbonyl
electrophiles
toward
enantioselective
desymmetrization
transformation.
The
were
readily
synthesized
by
incorporation
additional
base
sites
in
one
step.
efficiently
catalyzed
methanolytic
series
meso
cyclic
anhydrides
nearly
quantitative
yields
up
to
94%
ee.
In
contrast,
non-cage
analogues
simple
control
catalysts
showed
sluggish
conversion
much
lower
enantioselectivity.
Crystal
structure,
substrate
studies,
theoretical
modeling
consistently
suggested
essential
role
cage
harnessing
efficient
excellent
selectivity
control.
Язык: Английский
One-Pot Synthesis of Tridentate Bicyclocalixarene Cage Molecules
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 18, 2025
Efficient
one-pot
synthesis
of
tridentate
bicyclocalixarenes
was
developed
by
condensing
phloroglucinol
with
dechlorinated
pyrimidine
or
triazine
a
yield
up
to
58%.
These
cage-like
molecules
adopt
symmetric
three-blade
propeller
structure
different
terminal
function
groups
and
arm
spans
ranging
from
7.5
15.8
Å.
Due
the
1,3-alternate
configuration
intermediate
heterocalixarenes,
cage
can
be
prepared
only
benzene
rings
as
upper
lower
caps.
They
will
an
ideal
scaffold
for
preparation
ultrathin
two-dimensional
materials.
Язык: Английский
Solvent-mediated subcomponent self-assembly of covalent metallacycles for hierarchical porous materials synthesis
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
solvent-mediated
subcomponent
self-assembly
strategy
was
developed
for
synthesizing
covalent
metallacycles
with
different
shapes.
Язык: Английский
Revisiting the Origins of Reactivity and Selectivity in the Pd6L4-Cage-Catalyzed Diels–Alder Reactions: A Combined Computational and Experimental Study
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 11, 2025
Supramolecular
metal–organic
cages
(MOCs)
have
gained
attention
as
versatile
catalytic
platforms
due
to
their
self-assembled
architectures
and
well-defined
cavities,
which
mimic
enzyme
active
sites
enable
spatial
confinement.
This
confinement
modulates
the
reaction
pathways
enhances
performance.
Recent
studies
highlight
potential
in
various
organic
transformations,
but
factors
governing
MOC-catalyzed
reactions
remain
incompletely
understood.
work
builds
on
prior
computational
of
Diels–Alder
catalyzed
by
palladium-based
MOCs,
showing
that
common
view
transition-state
stabilization
via
π–π
interactions
is
not
valid.
Instead,
we
find
between
substrate
ligands
destabilize
transition
state.
Additionally,
theoretical
regioselectivity,
validated
experimentally,
suggest
encapsulation
efficiency
key
determining
selectivity.
These
findings
provide
new
insights
into
mechanisms
reactions.
Язык: Английский
Nickel (II) Macrocyclic Complexes: Template Synthesis, Spectroscopic Investigations, Electrochemical Behavior, DFT Studies, and Biological Evaluation
ChemistrySelect,
Год журнала:
2025,
Номер
10(15)
Опубликована: Апрель 1, 2025
Abstract
A
novel
series
of
tetraaza
nickel
(II)
macrocyclic
complexes
was
prepared
via
template
condensation
involving
the
ligand
2‐[4‐bromo‐2‐(2‐oxo‐1,2‐diphenyl‐ethylideneamino)‐phenylimino]‐1,2‐diphenyl‐ethanone
(ML)
and
selected
diamines,
such
as
4‐chloro
1,2‐phenylenediamine,
4‐bromo
1,2‐diaminotoluene,
4‐nitro
1,2‐diaminopropane,
ethylenediamine,
in
presence
NiCl
2
.6H
O.
The
its
resulting
were
characterized
through
elemental
analysis,
molecular
weight
determination,
a
range
spectral
techniques,
including
IR,
electronic
spectra,
1
H
NMR,
mass
spectrometry,
X‐ray
powder
diffraction,
DFT‐assisted
structural
characterization.
DFT
(TDDFT/B3LYP/6–311g(d)
method)
analysis
representative
Ni(II)
supports
plausible
structures
proposed
based
on
spectroscopic
studies.
These
analyses
suggest
that
each
complex
adopts
six‐coordinated
octahedral
geometry.
Their
redox
behavior
examined
detail
using
cyclic
voltammetry
(CV).
Furthermore,
new
tested
for
their
antimicrobial,
antioxidant,
antidiabetic,
antituberculosis
activities.
Antimicrobial
tests
conducted
against
E.
coli,
B.
subtilis,
A.
niger
,
P.
chrysogenum
synthesized
compounds.
antioxidant
properties
assessed
DPPH
assay
showed
[Ni(C
41
29
BrCl
N
4
)]
exhibited
highest
activity,
with
an
IC
50
value
89.13
mg/mL.
Additionally,
antimycobacterial
where
40
3
demonstrated
significant
effectiveness
inhibiting
growth
Mycobacterium
tuberculosis
.
Язык: Английский