Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 2, 2024
Abstract
The
efficient
construction
of
chalcogen‐atom‐based
chiral
compounds
remains
a
challenge,
despite
the
importance
organoselenium
and
organosulfur
in
life
materials
science.
Chalcogen
atoms
can
form
net
attractive
interactions
called
chalcogen
bonds,
but
it
is
an
undeveloped
tool
to
assist
asymmetric
catalysis.
Herein,
we
report
enantioselective
insertion
platform
install
stereogenic
center
bearing
selenyl
thiocyano
functional
groups.
Our
method
operates
by
synergistic
catalysis
guanidine
achiral
dirhodium
complex
three‐component
or
four‐component
reaction,
through
Se−S
bond
into
carbene
species,
competing
successfully
with
spontaneous
racemic
process
showing
high
regioselectivity.
As
elucidated
spectroscopic
experiments
computational
studies,
unique
mechanism
involving
as
well
hydrogen
bonding
was
established
account
for
enantiocontrol.
stereoselectivity
holds
broad
array
selenylthiocyanatopropanoates,
which
showed
excellent
anti‐inflammatory
toward
IL‐1β
low
cytotoxicity.
Dalton Transactions,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
article
explores
matere
bonds,
supported
by
theoretical
and
computational
studies.
These
σ-hole
interactions
with
group
7
elements
(Mn,
Tc,
Re)
are
key
in
crystal
engineering,
catalysis,
biological
systems.
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 976 - 981
Опубликована: Янв. 1, 2025
Triethoxysilane
was
found
to
be
an
efficient
catalyst
for
the
synthesis
of
E-alkenyl-
and
alkyl-di-boronate
esters
by
single
sequential
hydroboration
terminal
alkynes,
respectively,
with
pinacolborane.
Mechanistic
studies
support
that
formation
diboronate
proceeds
a
double
pathway
steric
electronic
profile
at
Si
being
key
enabling
second
step.
Weak
non-covalent
interactions
involving
C≡C
or
C═C
bonds
in
alkynes
alkenylboronate
have
been
identified
as
responsible
substrate
activation
toward
addition
HBPin.
Organic & Biomolecular Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Chalconium
and
halonium
salts
catalyze
Schiff
condensation.
Kinetic
data
DFT
calculations
show
that
the
catalytic
activity
correlates
with
maximum
electrostatic
potential
on
σ-holes,
whereas
other
factors
are
less
significant.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(43)
Опубликована: Май 24, 2024
The
ability
of
triaryltelluronium
salts
to
interact
with
N-halosuccinimides
(NXS)
through
chalcogen
bonding
(ChB)
in
the
solid
state
and
solution
is
demonstrated
herein.
Cocrystals
bearing
two
CF
Accounts of Chemical Research,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 25, 2024
ConspectusThe
development
of
supramolecular
chemistry
has
provided
a
variety
host
molecules
and
noncovalent
tools
for
boosting
catalytic
processes,
stimulating
the
emergence
advance
catalysis,
among
which
macrocyclic
cage-like
compounds
have
attracted
great
attention
due
to
their
possession
an
enzyme-mimetic
cavity
recognition
ability.
While
privileged
scaffolds
such
as
crown
ethers,
cyclodextrins,
cucurbiturils,
calixarenes,
metal-coordinated
cages
been
widely
used,
skeletons
usually
do
not
contain
directional
binding
site;
activation
mainly
rely
on
cation-associated
interactions
or
hydrophobic
effects.
In
this
context,
recent
anion
drawn
our
developing
recognition-directed
approach
by
using
tailor-made
functionalized
macrocycles
cages.
Anions
are
important
existing
species
in
both
biological
chemical
systems
play
role
regulating
structure
function
enzymes.
We
envisioned
that
taking
advantage
anions,
including
rich
variety,
diverse
geometry,
multiple
interaction
sites,
sophisticated
cooperation
can
be
manipulated
confined
directing
efficient
selective
catalysis.Following
concept,
we
initiated
study
introducing
typical
thiourea
H-bonding
groups
design
synthesize
series
bis-thiourea
macrocycles,
especially
chiral
incorporating
linkers.
Taking
obtained
strong,
cooperative
binding,
macrocycle-enabled
counteranion
trapping
strategy
was
developed,
afforded
greatly
enhanced
efficiency
excellent
stereocontrol
acid-catalyzing
reactions.
Furthermore,
inspired
sulfate-induced
dimerization
assembly,
built
substrate-induced
assembly
system,
enabling
induced-fit
network
enantioselective
catalysis.
addition,
recognition-driven
chirality
gearing
with
more
trithiourea
cage
revealed,
could
provide
basis
implementing
anion-triggered
allosteric
catalysis
within
induced
helical
space.
Not
limited
hydrogen
bonding,
emerging
anion-π
were
largely
exploited.
A
triazine-based
prism
containing
three
V-shaped
electron-deficient
π-cavities
constructed,
properties
studied.
Based
established
driving
highly
paved
way
push
toward
practical
useful
catalyst
design.These
results
demonstrated
anion-recognition
direction
serve
powerful,
versatile
It
is
feasible
only
employing
exogenous
anions
(e.g.,
counteranion)
handle
but
also
regulation
anionic
active
intermediates/transition
states,
from
use
conventional
recognition.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 2, 2024
The
efficient
construction
of
chalcogen-atom-based
chiral
compounds
remains
a
challenge,
despite
the
importance
organoselenium
and
organosulfur
in
life
materials
science.
Chalcogen
atoms
can
form
net
attractive
interactions
called
chalcogen
bonds,
but
it
is
an
undeveloped
tool
to
assist
asymmetric
catalysis.
Herein,
we
report
enantioselective
insertion
platform
install
stereogenic
center
bearing
selenyl
thiocyano
functional
groups.
Our
method
operates
by
synergistic
catalysis
guanidine
achiral
dirhodium
complex
three-component
or
four-component
reaction,
through
Se-S
bond
into
carbene
species,
competing
successfully
with
spontaneous
racemic
process
showing
high
regioselectivity.
As
elucidated
spectroscopic
experiments
computational
studies,
unique
mechanism
involving
as
well
hydrogen
bonding
was
established
account
for
enantiocontrol.
stereoselectivity
holds
broad
array
selenylthiocyanatopropanoates,
which
showed
excellent
anti-inflammatory
toward
IL-1β
low
cytotoxicity.
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.
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.
