Angewandte Chemie,
Год журнала:
2024,
Номер
136(36)
Опубликована: Июнь 6, 2024
Abstract
We
present
the
strategic
design
of
donor‐acceptor
cyanoarene‐based
photocatalysts
(PCs)
aiming
to
augment
beneficial
PC
degradation
for
halogen
atom
transfer
(XAT)‐induced
dehalogenation
reactions.
Our
investigation
reveals
a
competitive
nature
between
catalytic
cycle
and
pathway,
with
becoming
dominant,
particularly
less
activated
alkyl
halides.
The
behavior
PCs
significantly
impacts
efficiency
XAT
process,
leading
exploration
into
manipulating
in
desirable
direction.
Recognizing
variation
rate
degradation,
as
well
its
influence
on
reaction
across
range
structures,
we
carefully
engineered
develop
pre‐catalyst,
named
3DP‐DCDP‐IPN.
This
pre‐catalyst
undergoes
rapid
an
active
form,
3DP‐DCDP‐Me‐BN,
exhibited
enhanced
reducing
ability
radical
anion
form
induce
better
regeneration
consequently
effectively
catalyzes
reaction,
even
challenging
substrate.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(3), С. 1703 - 1708
Опубликована: Янв. 16, 2024
Visible-light-induced
three-component
1,2-alkylpyridylation
of
alkenes
with
unactivated
alkyl
iodides
and
aryl
cyanides
is
reported
via
a
photocatalytic
halogen-atom
transfer
(XAT)
strategy.
This
metal-free
protocol
utilizes
readily
available
tertiary
alkylamine
as
the
terminal
reductant
to
smoothly
convert
into
corresponding
carbon
radical
species.
The
reaction
features
broad
substrate
scope,
excellent
functional
group
tolerance,
high
efficiency,
mild
conditions.
practicability
this
methodology
further
demonstrated
in
late-stage
difunctionalization
bioactive
molecules.
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.
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.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 7, 2025
Comprehensive
Summary
Cross‐coupling
reactions
between
aryl
halides
and
thiolates
or
selenolates
typically
require
transition
metals,
photocatalysts,
strong
bases,
or/and
malodorous
thiols/selenols,
with
various
mechanisms
proposed.
This
study
aims
to
leverage
a
new
application
of
neutral
ChB
address
these
challenges
enable
very
simple
photoinduced
cross‐electrophile
C—S/Se
coupling
using
readily
available
chalcogen
electrophiles.
Mechanistic
investigations
have
revealed
the
important
role
in
facilitating
single
electron
transfer
processes,
thereby
enabling
generation
thiolates/selenolates
from
stable
electrophiles
α
‐aminoalkyl
radicals,
which
possess
capability
abstract
halogen
atoms
iodides.
Moreover,
provided
support
for
radical
nucleophilic
substitution
mechanism.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 24, 2025
A
photoinduced
and
catalyst-free
radical
cyclization
process
for
the
synthesis
of
3,3-disubstituted
oxindoles
is
reported.
This
method
utilizes
readily
available
α-bromoanilides
as
substrates,
showcasing
a
broad
substrate
scope.
The
reaction
mechanism
facilitated
by
photoactivated
charge
transfer
complex
based
on
halogen
bonding
α-bromoanilide
with
TMG
alcohol.
Abstract
Catalytic
activation
of
C
aryl
‐O
bonds
is
considered
as
a
powerful
strategy
for
the
production
aromatics
from
lignin.
However,
due
to
high
reduction
potentials
diaryl
ether
4‐O‐5
linkage
models,
their
single
electron
remains
daunting
challenge.
This
study
presents
blue
light‐induced
bifunctional
N‐heterocyclic
carbene
(NHC)‐catalyzed
one‐electron
models
synthesis
trivalent
phosphines.
The
H‐bond
between
newly
devised
NHC
and
ethers
responsible
success
transfer.
Furthermore,
this
approach
demonstrates
selective
unsymmetric
ethers,
oligomeric
phenylene
oxide,
lignin
model.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июнь 6, 2024
We
present
the
strategic
design
of
donor-acceptor
cyanoarene-based
photocatalysts
(PCs)
aiming
to
augment
beneficial
PC
degradation
for
halogen
atom
transfer
(XAT)-induced
dehalogenation
reactions.
Our
investigation
reveals
a
competitive
nature
between
catalytic
cycle
and
pathway,
with
becoming
dominant,
particularly
less
activated
alkyl
halides.
The
behavior
PCs
significantly
impacts
efficiency
XAT
process,
leading
exploration
into
manipulating
in
desirable
direction.
Recognizing
variation
rate
degradation,
as
well
its
influence
on
reaction
across
range
structures,
we
carefully
engineered
develop
pre-catalyst,
named
3DP-DCDP-IPN.
This
pre-catalyst
undergoes
rapid
an
active
form,
3DP-DCDP-Me-BN,
exhibited
enhanced
reducing
ability
radical
anion
form
induce
better
regeneration
consequently
effectively
catalyzes
reaction,
even
challenging
substrate.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(14), С. 10004 - 10011
Опубликована: Июнь 27, 2024
-Alkoxyphthalimides,
one
kind
of
phthalimide
derivative,
have
great
importance
in
synthesis,
mainly
used
as
free
radical
precursors.
While
the
unit,
for
a
long
time,
was
treated
part
waste
stream.
Construction
C-N
bonds
has
always
been
hot
spot,
especially
reductive
cross-coupling.
Herein,
nickel-catalyzed
cross-coupling
reaction
The
functionalization
of
the
C-Cl
bond
in
unactivated
aryl
chlorides
under
mild
conditions
presents
a
significant
challenge.
We
disclose
general
protocol
for
constructing
both
partially
and
entirely
unsymmetrical
tertiary
phosphines
through
Pd/keYPhos-catalyzed
coupling
with
secondary
conditions.
reaction
exhibits
excellent
functional
group
tolerance
broad
substrate
scopes.
Furthermore,
rapid
synthesis
ligands
luminescent
compound
sTPPs,
alongside
gram-scale
systhesis,
demonstrates
practical
applicability
this
method.
Molecular Physics,
Год журнала:
2024,
Номер
unknown
Опубликована: Май 24, 2024
Phosphorus-centered
pnictogen
bonds,
similar
to
well-studied
halogen
play
a
vital
role
in
molecular
recognition
and
assembly.
This
study
aims
explain
how
bonds
interact
with
other
noncovalent
interactions.
A
model
system,
phosphines
(PH3),
which
is
also
present
phosphorus
cycles
reduces
planetary
atmospheres,
examined.
The
investigation
of
the
trifluoride
(PF3)
molecule
explores
its
substituent
effects.
To
generate
broad
spectrum
configurations,
specially
tailored
protocol
for
sampling
optimisation
was
implemented.
configurations
were
refined
uncover
primary
interaction
patterns,
clustering
algorithm
revealed
unique
patterns.
report
presents
energy
stability
distribution
all
clusters.
Our
findings
verify
prevalent
presence
identified
by
their
geometric
characteristics
co-occurrence
hydrogen
show
an
almost
linear
correlation.
Another
significant
discovery
correlation
between
various
decomposition
elements,
especially
regarding
electrostatic
overall
binding
energy.
These
results
are
anticipated
significantly
contribute
towards
our
comprehension
non-covalent
interactions
among
phosphorus-containing
molecules
formulation
empirical
models
having
physical
interpretations.
