Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(26), P. 7291 - 7303
Published: Jan. 1, 2023
Herein
we
report
a
cobalt-catalyzed
enantioselective
C-H/N-H
annulation
of
aryl
sulfonamides
with
allenes
and
alkynes,
using
either
chemical
or
electrochemical
oxidation.
By
O2
as
the
oxidant,
proceeds
efficiently
low
catalyst/ligand
loading
5
mol%
tolerates
wide
range
allenes,
including
2,3-butadienoate,
allenylphosphonate,
phenylallene,
resulting
in
C-N
axially
chiral
sultams
high
enantio-,
regio-,
position
selectivities.
The
alkynes
also
exhibits
excellent
enantiocontrol
(up
to
>99%
ee)
variety
functional
sulfonamides,
internal
terminal
alkynes.
Furthermore,
oxidative
is
achieved
simple
undivided
cell,
demonstrating
versatility
robustness
cobalt/Salox
system.
gram-scale
synthesis
asymmetric
catalysis
further
highlight
practical
utility
this
method.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
52(23), P. 8106 - 8125
Published: Jan. 1, 2023
This
tutorial
review
delves
into
the
unique
advantages
of
electrochemistry
in
context
asymmetric
catalysis,
first
providing
a
brief
introduction
to
electrosynthesis,
then
exploring
representative
case
studies
with
mechanistic
focus.
Small,
Journal Year:
2023,
Volume and Issue:
19(49)
Published: Aug. 23, 2023
Space
charge
transfer
of
heterostructures
driven
by
the
work-function-induced
built-in
field
can
regulate
electronic
structure
catalysts
and
boost
catalytic
activity.
Herein,
an
epitaxial
heterojunction
catalyst
CoO/Mo2
C
with
interfacial
electron
redistribution
induced
work
functions
(WFs)
is
constructed
for
overall
water
splitting
via
a
novel
top-down
strategy.
Theoretical
simulations
experimental
results
unveil
that
WFs-induced
facilitates
from
CoO
to
Mo2
through
formed
"Co─C─Mo"
bond
at
interface
C,
achieving
redistribution,
further
optimizing
Gibbs
free
energy
primitive
reaction
step
then
accelerating
kinetics
hydrogen
evolution
(HER).
As
expected,
effects
exhibits
excellent
HER
activity
only
needing
overpotential
107
mV
achieve
10
mA
cm-2
stability
60-h
continuous
catalyzing.
Besides,
assembled
behaves
outstanding
performance
toward
(1.58
V
).
This
provides
possibility
designing
materials
based
on
arising
application
in
other
fields.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Sept. 14, 2023
Organic
electrocatalytic
conversion
is
an
essential
pathway
for
the
green
of
low-cost
organic
compounds
to
high-value
chemicals,
which
urgently
demands
development
efficient
electrocatalysts.
Here,
we
report
a
Cu
single-atom
dispersed
Rh
metallene
arrays
on
foam
cathodic
nitrobenzene
electroreduction
reaction
and
anodic
methanol
oxidation
reaction.
In
coupled
system,
Cusingle-atom-Rh
requires
only
low
voltages
1.18
V
reach
current
densities
100
mA
cm-2
generating
aniline
formate,
with
up
~100%
conversion/
selectivity
over
~90%
formate
Faraday
efficiency,
achieving
synthesis
chemicals.
Density
functional
theory
calculations
reveal
electron
effect
between
host
catalytic
mechanism.
The
synergistic
H*-spillover
can
improve
process
reduce
energy
barrier
process,
thus
enhancing
activity
target
product
selectivity.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Aug. 29, 2023
The
N-N
atropisomer,
as
an
important
and
intriguing
chiral
system,
was
widely
present
in
natural
products,
pharmaceutical
lead
compounds,
advanced
material
skeletons.
anisotropic
structural
characteristics
caused
by
its
special
axial
rotation
have
always
been
one
of
the
challenges
that
chemists
strive
to
overcome.
Herein,
we
report
efficient
method
for
enantioselective
synthesis
axially
frameworks
via
a
cobalt-catalyzed
atroposelective
C-H
activation/annulation
process.
reaction
proceeds
under
mild
conditions
using
Co(OAc)2·4H2O
catalyst
with
salicyl-oxazoline
(Salox)
ligand
O2
oxidant,
affording
variety
products
high
yields
enantioselectivities.
This
protocol
provides
approach
facile
construction
atropisomers
further
expands
range
derivatives.
Additionally,
electrocatalysis,
desired
were
also
successfully
achieved
good
excellent
efficiencies
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(45)
Published: Sept. 20, 2023
Pyridine
oximes
produced
from
aldehyde
or
ketone
with
hydroxylamine
(NH2
OH)
have
been
widely
applied
in
pharmaceutics,
enzymatic
and
sterilization.
However,
the
important
raw
material
NH2
OH
exhibits
corrosive
unstable
properties,
leading
to
substantial
energy
consumption
during
storage
transportation.
Herein,
this
work
presents
a
novel
method
for
directly
synthesizing
highly
valuable
pyridine
using
situ
generated
electrocatalytic
NO
reduction
well-design
nanofiber
membranes
(Al-NFM)
derived
-MIL-53(Al).
Particularly,
2-pyridinealdoxime,
precursor
of
antidote
pralidoxime
(2-PAM)
nerve
agents
suffering
scarcity
high
cost,
was
achieved
Faraday
efficiency
up
49.8
%
yield
92.1
%,
attributing
selectivity
production
on
Al-NFM,
further
easily
reacted
iodomethane
produce
2-PAM.
This
study
proposes
creative
approach,
having
wide
universality
other
range
functional
groups,
which
not
only
facilitates
conversion
exhaust
gas
(NO)
waste
water
(NO2-
)
into
chemicals
especially
utilization
through
electrochemistry,
but
also
holds
significant
potential
synthesis
neuro
detoxifying
drugs
humanity
security.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(21), P. 11518 - 11523
Published: May 16, 2023
The
first
examples
of
enantioselective
doubly
decarboxylative
cross
coupling
are
disclosed.
Malonate
half
amides
smoothly
coupled
to
a
variety
primary
carboxylic
acids
after
formation
the
corresponding
redox-active
esters
under
Ni-electrocatalytic
conditions
using
new
chiral
ligand
based
on
PyBox,
resulting
in
with
α-alkylated
stereocenters.
scope
reaction
is
broad,
tolerating
numerous
functional
groups,
and
uniformly
proceeds
high
ee.
Finally,
potential
utility
this
radical–radical
reductive
simplify
synthesis
demonstrated
case
studies.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(45)
Published: Sept. 12, 2023
Despite
widespread
use
of
the
deuterium
isotope
effect,
selective
labeling
chemical
molecules
remains
a
major
challenge.
Herein,
facile
and
general
electrochemically
driven,
organic
mediator
enabled
deuteration
styrenes
with
oxide
(D2
O)
as
economical
source
was
reported.
Importantly,
this
transformation
could
be
suitable
for
various
electron
rich
mediated
by
triphenylphosphine
(TPP).
The
reaction
proceeded
under
mild
conditions
without
transition-metal
catalysts,
affording
desired
products
in
good
yields
excellent
D-incorporation
(D-inc,
up
to
>99
%).
Mechanistic
investigations
means
experiments
cyclic
voltammetry
tests
provided
sufficient
support
transformation.
Notably,
method
proved
powerful
tool
late-stage
biorelevant
compounds.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(20), P. 10967 - 10973
Published: April 19, 2023
Despite
the
widespread
applications
of
α-hydroxyalkyl
cyclic
amines,
direct
and
diverse
access
to
such
a
class
unique
vicinal
amino
alcohols
still
remains,
date,
challenge.
Here,
through
strategy
electroreductive
α-hydroxyalkylation
inactive
N-heteroarenes
with
ketones
or
electron-rich
arylaldehydes,
we
describe
room
temperature
approach
for
construction
which
features
broad
substrate
scope,
operational
simplicity,
high
chemoselectivity,
no
need
pressurized
H2
gas
transition
metal
catalysts.
The
zinc
ion
generated
from
anode
oxidation
plays
crucial
role
in
activation
both
reactants
by
decreasing
their
reduction
potentials.
electroreduction
combination
Lewis
acids
this
work
is
anticipated
develop
more
useful
transformations.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(9), P. 4349 - 4373
Published: Jan. 1, 2024
Contact-electro-catalysis
(CEC)
is
an
emerging
field
that
utilizes
electron
transfer
occurring
at
the
liquid–solid
and
even
liquid–liquid
interfaces
because
of
contact-electrification
effect
to
stimulate
redox
reactions.