ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
15(3), P. 2212 - 2221
Published: Jan. 23, 2025
Despite
recent
advances
in
enantioselective
radical
coupling
with
strained
cyclic
rings,
asymmetric
reactions
triggered
by
unstrained
motifs
remain
rare.
Herein,
we
report
a
mild
and
general
strategy
for
activating
diverse
set
of
readily
available
alcohols
the
remote
site-specific
allylic
alkylation
ketones
through
combination
photoredox-mediated
proton-coupled
electron
transfer
chiral
chromium
catalysis.
This
newly
developed
dual
catalytic
system
exhibits
extensive
applicability,
operates
under
conditions,
offers
straightforward
operation,
demonstrates
tolerance
to
functional
groups.
The
open-shell
has
also
been
applied
late-stage
modification
complex
drug
natural
product
derivatives
high
levels
enantioselectivity.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 4665 - 4680
Published: March 5, 2025
Transition
metal
catalysis
is
an
indispensable
tool
for
organic
synthesis
that
has
been
harnessed,
modulated,
and
perfected
many
decades
by
careful
selection
of
centers
ligands,
giving
rise
to
synthetic
methods
with
unparalleled
efficiency
chemoselectivity.
Recent
developments
have
demonstrated
how
light
irradiation
can
also
be
recruited
as
a
powerful
dramatically
alter
the
outcome
catalytic
reactions,
providing
access
innovative
pathways
remarkable
potential.
In
this
context,
adoption
photochemical
conditions
mainstream
strategy
drive
reactions
unveiled
exciting
opportunities
exploit
rich
excited-state
framework
transition
metals
applications.
This
Perspective
examines
advances
in
application
complexes
standalone
photocatalysts,
exploiting
innate
reactivity
their
excited
states
beyond
common
use
photoredox
catalysts.
An
account
relevant
examples
dissected
provide
discussion
on
electronic
reorganization,
orbitals
involved,
associated
different
types
states.
analysis
aims
practitioners
fundamental
principles
guiding
strategies
understand,
design,
apply
light-activation
homogeneous
synthesis.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
57(13), P. 1827 - 1838
Published: June 21, 2024
ConspectusChemists
have
long
been
inspired
by
biological
photosynthesis,
wherein
a
series
of
excited-state
electron
transfer
(ET)
events
facilitate
the
conversion
low
energy
starting
materials
such
as
H
The Journal of Physical Chemistry Letters,
Journal Year:
2024,
Volume and Issue:
15(16), P. 4367 - 4374
Published: April 15, 2024
Understanding
deracemization
is
crucial
for
progress
in
chiral
chemistry,
especially
improving
separation
techniques.
Here,
we
first
report
the
phenomenon
of
flipping
(or
reverse
deracemization)
a
material
(i.e.,
sodium
chlorate
crystals)
during
Viedma
deracemization,
employing
small-volume
reactor
system
precise
analysis.
We
observe
considerable
flipping,
influenced
by
initial
imbalance
numbers
L-
and
D-form
particles.
developed
simple
probabilistic
model
to
further
elucidate
this
behavior.
find
that
fluctuation
populations
crystal
particles
resulting
from
their
random
dissolution
regeneration
key
factor
behind
flipping.
This
study
not
only
brings
light
intriguing
observation
but
also
contributes
enhancement
JACS Au,
Journal Year:
2024,
Volume and Issue:
4(12), P. 4899 - 4909
Published: Nov. 21, 2024
Nitroaromatics,
as
an
important
member
and
source
of
nitrogen-containing
aromatics,
is
bringing
enormous
economic
benefits
in
fields
pharmaceuticals,
dyes,
pesticides,
functional
materials,
fertilizers,
explosives.
Nonetheless,
the
notoriously
polluting
nitration
industry,
which
suffers
from
excessive
discharge
fumes
waste
acids,
poor
group
tolerance,
tremendous
purification
difficulty,
renders
mild,
efficient,
environmentally
friendly
a
formidable
challenge.
Herein,
we
develop
visible-light-driven
biocompatible
arene
C–H
strategy
with
good
efficiency
regioselectivity,
marvelous
substrate
applicability
wide
application
scale-up
synthesis,
total
late-stage
functionalization.
A
nitryl
radical
delivered
through
unusual
β-homolysis
photoexcited
ferric-nitrate
complex
proposed
to
be
key
nitrification
reagent
this
system.
Living
biological
systems
rely
on
the
continuous
operation
of
chemical
reaction
networks.
These
networks
sustain
out-of-equilibrium
regimes
in
which
energy
is
continually
converted
into
controlled
mechanical
work
and
motion.
Out-of-equilibrium
have
also
enabled
design
successful
development
artificial
autonomously
operating
molecular
machines,
comprising
pairs
formally—but
non-microscopically—reverse
pathways
drive
motion
at
level.
In
systems,
concurrent
multiple
by
chemoselectivity
enzymes
their
co-factors,
nature’s
dissipative
involve
several
classes
reactions.
contrast,
reactivity
that
has
been
harnessed
to
develop
pursuit
machines
limited
a
single
type.
Only
small
number
synthetic
exhibit
chemically
fuelled
molecular-level
motion,
all
exploit
same
class
acylation–hydrolysis
reaction.
Here
we
show
redox
network,
oxidation
reduction
pathways,
can
autonomous
unidirectional
about
C–C
bond
most
structurally
simple
motor
yet
reported,
an
achiral
biphenyl.
The
combined
use
oxidant
reductant
as
fuels,
directionality
motor,
are
both
exploiting
enantioselectivity
functional
separation
inherent
enzyme
catalysis.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(17), P. 3530 - 3535
Published: April 24, 2024
State-of-the-art
strategies
for
alkene-hydroxyazidation,
which
yield
a
mixture
of
β-azido
alcohol
and
peroxide,
must
rely
on
phosphine
reagents
to
improve
the
chemoselectivity.
To
overcome
above
problems,
we
present
photochemical
hydroxyazidation
alkenes
via
Mn-mediated
ligand-to-metal
charge
transfer
(LMCT)
in
O
