Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 20, 2024
Complexity-generating
reactions
that
access
three-dimensional
products
from
simple
starting
materials
offer
substantial
value
for
drug
discovery.
While
oxygen-containing
heterocycles
frequently
feature
unique,
nonaromatic
architectures
such
as
spirocyclic
rings,
exploration
of
these
chemical
spaces
is
limited
by
conventional
synthetic
approaches.
Herein,
we
report
a
copper-catalyzed
annulation
and
alkene
transposition
cascade
reaction
enables
modular
preparation
complex,
ethers
readily
available
alkenol
substrates
via
transannular
1,5-hydrogen
atom
transfer-mediated
C–H
functionalization.
Our
transformation
displays
broad
substrate
scope,
shows
excellent
heteroatom
compatibility,
constructs
spirocycles
varying
ring
sizes.
The
wider
utility
this
method
highlighted
numerous
product
diversifications
short
synthesis
the
all-carbon
framework
spirotenuipesine
A.
We
anticipate
can
significantly
streamline
to
privileged
class
will
find
application
in
natural
synthesis.
Alternating
current
electrolysis
has
emerged
as
a
promising
technique
for
addressing
challenging
redox
reactions
that
are
otherwise
difficult
or
impossible
direct
electrolysis.
Under
mild
and
transition-metal-free
reaction
conditions,
general
electrochemical
denitrative
cyclization
of
nitroarenes
was
developed
to
access
various
cyclic
sulfone-containing
derivatives
biological
significance.
The
key
success
lies
in
the
facile
manipulation
multiple
events
upon
rapid
alternating
polarity
switching
enhance
selectivity
efficiency.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 13, 2024
ConspectusElectrochemistry
has
been
used
as
a
tool
to
drive
chemical
reactions
for
more
than
two
centuries.
With
the
help
of
an
electrode
and
power
source,
chemists
are
provided
with
system
whose
potential
can
be
precisely
dialed
in.
The
theoretically
infinite
redox
range
renders
electrochemistry
capable
oxidizing
or
reducing
some
most
tenacious
compounds.
Indeed,
electroreduction
offers
alternative
generating
highly
active
intermediates
from
electrophiles
(e.g.,
halides,
alkenes,
etc.)
in
organic
synthesis,
which
untouchable
traditional
reduction
methods.
Meanwhile,
reductive
coupling
extensively
utilized
both
industrial
academic
settings
due
their
ability
swiftly,
accurately,
effectively
construct
C–C
C–X
bonds,
present
innovative
approaches
synthesizing
complex
molecules.
Nonetheless,
its
application
is
constrained
by
several
inherent
limitations:
(a)
requirement
stoichiometric
quantities
agents,
(b)
scarce
activation
strategies
inert
substrates
high
potentials,
(c)
incomplete
mechanistic
elucidation,
(d)
challenges
isolation
intermediates.
merging
represents
attractive
approach
address
above
limitations
synthesis
seen
increasing
use
synthetic
community
over
past
few
years.Since
2020,
our
group
dedicated
developing
electroreductive
cross-coupling
using
readily
available
small
molecules,
such
arenes,
CO2,
D2O,
value-added
products.
Electroreductive
chemistry
versatile
powerful
capacity
precise
selectivity
control,
allowed
us
develop
three
electrochemical
modes
lab:
(1)
An
economically
advantageous
direct
(EDR)
strategy
that
emphasizes
efficiency,
achieves
atom
utilization,
minimizes
unnecessary
atomic
waste.
(2)
A
class
organo-mediated
(EOMR)
methods
controlling
reaction
pathways.
This
allows
modulation
processes
enhance
efficiency
selectivity.
(3)
metal-catalyzed
(EMCR)
method
enables
selective
functionalization
specific
bonds
functional
groups
under
mild
conditions,
thereby
occurrence
side
reactions.
We
commenced
studies
establishing
organic-mediator-promoted
carboxylation
aryl
alkyl
halides.
was
then
employed
arylcarboxylation
simple
styrenes
halides
manner.
electrolysis
arenes
epoxides
CO2
carboxyl
source
achieved.
Moreover,
through
adjustment
we
successfully
accomplished
deuteration
olefins,
unactivated
enabling
efficient
formation
D-labeled
Finally,
building
on
previous
understanding
developed
series
alkylation
enable
C(sp3)–C(sp3)
Advanced Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 21, 2025
Partial
oxidation
of
methane
(POM)
is
achieved
by
forming
air-methane
microbubbles
in
saltwater
to
which
an
alternating
electric
field
applied
using
a
copper
oxide
foam
electrode.
The
solubility
increased
putting
it
contact
with
water
containing
dissolved
KCl
or
NaCl
(3%).
Being
fully
dispersed
as
(20-40
µm
diameter),
reacts
more
hydroxyl
radicals
(OH·)
at
the
gas-water
interface.
voltage
(100
mV)
generates
two
synergistic
POM
processes
dominated
Cl-
→
Cl·
+
e-
and
O2
-•
under
positive
negative
potentials,
respectively.
By
tuning
frequency
amplitude,
extent
path
process
can
be
precisely
controlled
so
that
than
90%
methanol
selectively
formed
compared
byproducts,
dichloromethane,
acetic
acid.
conversion
yield
estimated
57%
rate
approximately
887
µM
h-1.
This
method
appears
have
potential
for
removing
from
air
seawater
converting
higher-concentration
sources
into
value-added
methanol.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
In
this
study,
a
straightforward
and
environmentally
benign
electrochemical
mono-functionalization
of
alkenes
has
been
established
for
the
synthesis
alkenyl
selenium
sulfonates
using
elemental
as
source.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 25, 2025
The
direct
functionalization
of
alkyne
triple
bonds
using
a
radical
strategy
provides
an
efficient
platform
for
creating
wide
range
substituted
alkenes.
However,
developing
multicomponent
enantioselective
reaction
feedstock
alkynes
to
forge
all-carbon
quaternary
stereocenters─while
addressing
challenges
related
compatibility,
selectivity,
and
efficiency─remains
relatively
rare.
Here
we
report
electrochemical
nickel-catalyzed
three-component
cross-coupling
readily
available
terminal
alkynes,
diverse
racemic
alkyl
precursors,
group
transfer
reagents
(such
as
(TMS)3Si-H,
RSe-SeR,
RTe-TeR,
CHI3),
achieving
excellent
regio-,
stereo-,
enantioselectivities
(more
than
70
examples,
up
95%
ee).
Electricity-mediated
difunctionalizations
significantly
expand
the
scope
both
aliphatic
aromatic
demonstrating
functional
compatibility.
key
success
lies
in
rational
design
anodically
generated
nickel-bound
tertiary
intermediates,
which
stereoselectively
capture
form
vinyl
radicals
participate
subsequently
processes
enable
intermolecular
anti-stereoselective
difunctionalization
alkynes.
This
approach
allows
transformation
into
structural
entities
with
α-quaternary
stereogenic
centers.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 8, 2024
During
chemical
reactions,
especially
for
electrocatalysis
and
electrosynthesis,
the
electric
field
is
most
central
driving
force
to
regulate
reaction
process.
However,
due
difficulty
of
quantitatively
measuring
effects
caused
at
microscopic
level,
regulation
electrocatalytic
reactions
by
fields
has
not
been
well
digitally
understood
yet.
Herein,
we
took
infrared/Raman
spectral
signals
CO
ACS Applied Materials & Interfaces,
Год журнала:
2024,
Номер
16(36), С. 47368 - 47377
Опубликована: Авг. 27, 2024
Metal
alloys
not
only
increase
the
composition
and
spatial
distribution
of
elements
but
also
provide
opportunity
to
adjust
their
physicochemical
properties.
Recently,
multimetallic
alloy
nanocatalysts
have
attracted
great
attention
in
energy
applications
chemical
industry.
This
work
presents
production
three
ternary
PdCuSn
nanocrystalline
assemblies
with
similar
compositions
via
a
one-step
hydrothermal
method.
The
shape
variation
assembly
units
from
nanosheets
nanowires
nanoparticles
were
realized
by
adjusting
percentage
Sn
metal
precursors.
Experimental
data
show
that
nanowire
networks
showed
best
catalytic
activity
virtue
optimized
morphological
characteristics
microscopic
electronic
structure.
With
electrooxidation
methanol,
ethanol,
ethylene
glycol,
glycerol
at
30
°C,
demonstrated
1129,
2111,
2540,
1445
mA
mg
