A Fluorogenic Substrate for Quinoline Reduction: Pnictogen‐Bonding Catalysis in Aqueous Systems
Helvetica Chimica Acta,
Год журнала:
2024,
Номер
107(5)
Опубликована: Март 6, 2024
Abstract
It
is
often
said
that
pnictogen‐bonding
catalysis,
and
σ
‐hole
catalysis
in
general,
would
not
work
aqueous
systems
because
the
solvent
interfere
as
an
overcompetitive
pnictogen‐bond
acceptor.
In
this
study,
we
show
transfer
of
from
hydrophobic
solvents
to
possible
by
replacing
only
with
hydrophilic
substrates,
without
changing
catalyst
or
reaction.
This
differs
conventional
covalent
Lewis
acid
catalysts,
which
are
instantaneously
destroyed
ligand
exchange.
With
their
water‐proof
substituents
place
exchangeable
ligands,
supramolecular
counterpart
evinced
catalyze
hydrogenation
quinolines
neutral
systems.
To
secure
these
results,
introduce
a
water‐soluble
fluorogenic
substrate
releases
coumarin
upon
reduction
instead
activated
quinolidiniums,
stiborane
catalysts
deepened
holes.
They
demonstrate
can
operate
higher‐order
architectures
for
under
biologically
relevant
conditions,
provide
operational
assay
high‐throughput
screening
fluorescence
imaging,
situ
conditions.
Язык: Английский
Pnictogen‐Bonding Enzymes
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(45)
Опубликована: Июль 5, 2024
Abstract
The
objective
of
this
study
was
to
create
artificial
enzymes
that
capitalize
on
pnictogen
bonding,
a
σ‐hole
interaction
is
essentially
absent
in
biocatalysis.
For
purpose,
stibine
catalysts
were
equipped
with
biotin
derivative
and
combined
streptavidin
mutants
identify
an
efficient
transfer
hydrogenation
catalyst
for
the
reduction
fluorogenic
quinoline
substrate.
Increased
catalytic
activity
from
wild‐type
best
coincides
depth
σ
hole
Sb(V)
center,
emergence
saturation
kinetic
behavior.
Michaelis–Menten
analysis
reveals
transition‐state
recognition
low
micromolar
range,
more
than
three
orders
magnitude
stronger
millimolar
substrate
recognition.
Carboxylates
preferred
by
contribute
hydrogen‐bonded
ion
pairing
anion‐π
interactions
emerging
pyridinium
product.
challenging
stereoselectivity
aqueous
systems
further
emphasizes
compatibility
bonding
higher
order
catalysis.
Язык: Английский
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
Pnictogen‐Bonding Enzymes
Angewandte Chemie,
Год журнала:
2024,
Номер
136(45)
Опубликована: Июль 5, 2024
Abstract
The
objective
of
this
study
was
to
create
artificial
enzymes
that
capitalize
on
pnictogen
bonding,
a
σ‐hole
interaction
is
essentially
absent
in
biocatalysis.
For
purpose,
stibine
catalysts
were
equipped
with
biotin
derivative
and
combined
streptavidin
mutants
identify
an
efficient
transfer
hydrogenation
catalyst
for
the
reduction
fluorogenic
quinoline
substrate.
Increased
catalytic
activity
from
wild‐type
best
coincides
depth
σ
hole
Sb(V)
center,
emergence
saturation
kinetic
behavior.
Michaelis–Menten
analysis
reveals
transition‐state
recognition
low
micromolar
range,
more
than
three
orders
magnitude
stronger
millimolar
substrate
recognition.
Carboxylates
preferred
by
contribute
hydrogen‐bonded
ion
pairing
anion‐π
interactions
emerging
pyridinium
product.
challenging
stereoselectivity
aqueous
systems
further
emphasizes
compatibility
bonding
higher
order
catalysis.
Язык: Английский
Research Progress on Anion-π Interactions
Chinese Journal of Organic Chemistry,
Год журнала:
2024,
Номер
44(4), С. 1181 - 1181
Опубликована: Янв. 1, 2024
Anion-π
interaction
is
a
non-covalent
in
host-guest
chemistry.In
general,
aromatic
π-systems
are
regarded
as
electron
rich
and
may
have
repulsive
interactions
with
negatively
charged
systems.Therefore,
the
anion-π
interaction,
which
seems
counterintuitive,
has
attracted
remarkable
attention
since
it
was
first
reported.And
surprisingly,
shown
broad
significant
potential
applications
various
fields,
including
molecular
recognition,
catalysis,
self-assembly,
aggregation-induced
luminescent
materials,
design
synthesis
of
novel
anionic
receptors.This
review
focuses
on
research
progress
fields
theoretical
studies,
receptor
synthesis,
luminescence
last
decade.Finally,
application
prospects
field
supramolecular
chemistry
will
be
provided.
Язык: Английский
Anion–π catalysis on carbon allotropes
Beilstein Journal of Organic Chemistry,
Год журнала:
2023,
Номер
19, С. 1881 - 1894
Опубликована: Дек. 12, 2023
Anion–π
catalysis,
introduced
in
2013,
stands
for
the
stabilization
of
anionic
transition
states
on
π-acidic
aromatic
surfaces.
catalysis
carbon
allotropes
is
particularly
attractive
because
high
polarizability
promises
access
to
really
strong
anion–π
interactions.
With
these
expectations,
fullerenes
has
been
2017,
followed
by
nanotubes
2019.
Consistent
with
expectations
from
theory,
generally
increases
polarizability.
Realized
examples
reach
enolate
addition
chemistry
asymmetric
Diels–Alder
reactions
and
autocatalytic
ether
cyclizations.
Currently,
gains
momentum
combination
electric-field-assisted
transformative
impact
organic
synthesis.
Язык: Английский