Research Square (Research Square),
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 10, 2024
Abstract
Deuterated
N-heteroarenes
offer
vital
applications
in
pharmaceutical
and
material
fields
(e.g.,
psychotropic
drugs
deuterated
OLEDs)1,2.
However,
their
synthesis
from
hydrogen
isotope
exchange
(HIE)
reactions
always
requires
expensive
isotopic
reagents
(D2,
C2H5OD,
C6D6),
metal
complexes,
or
hazardous
conditions
(≥
120
oC
/
20
bar
H2).
Here
we
demonstrate
a
novel
route
for
via
single-atom
photocatalysis
(Pd1/TiO2)
conducted
D2O
at
room
temperature
under
410
nm
irradiation
inert
atmosphere.
This
protocol
successfully
afforded
satisfactory
deuteration
of
46
N-heteroarenes.
By
recycling
used
photocatalysts/D2O,
up
to
1.157
kg
(11.93
mol)
90%
D
incorporation)
were
yielded
using
only
4.5
L
(249
mol).
Mechanism
investigations
revealed
that
partially
reduced
Pd
species,
in
situ
generated
light
irradiation,
active
sites
photocatalytic
HIE.
The
scalable
selective
SA
mild
described
herein
will
feasible
effective
path
developing
small-molecule
electronic
materials.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 4, 2025
Traditional
reductions
of
alkenes,
such
as
using
stoichiometric
reductants
with
waste
generation
and
catalytic
hydrogenation
high-pressure
H2,
are
accompanied
by
environmental
or
safety
issues.
Herein,
we
demonstrated
a
universal
method
for
the
electrocatalytic
deuteration
alkenes
modified
electrodes
under
ambient
temperature.
The
key
M-H/M-D
species
alkene
reduction
were
generated
from
electrolysis
H2O/D2O
on
electrodes,
which
avoided
usage
H2
D2.
Mono-,
di-,
tri-,
tetra-substituted
successfully
reduced
in
this
system
H2O
D2O
hydrogen
deuterium
sources.
Electron-donating/-withdrawing
other
easily
reducible
functional
groups,
complicated
natural
products
drugs
all
reductive
hydrogenated
deuterated
excellent
yields
(85
examples,
up
to
99%).
Faraday
efficiency
efficient
could
reach
84%.
Moreover,
amount
metal
decrease
less
than
0.01
mol
%.
Chemical Society Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
This
review
highlights
organo-mediators
that
enable
electrochemical
reactions
via
outer-sphere
electron
transfer
(ET),
offering
advantages
such
as
availability,
tunability,
and
simplified
post-processing
compared
to
direct
electrolysis.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 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)
Chinese Journal of Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 16, 2025
Comprehensive
Summary
The
N–H
methylsulfoxidation
of
sulfoximines
using
DMSO
as
a
methylsulfinyl
source,
induced
by
electrochemistry,
has
been
developed.
This
method
is
the
first
example
an
electrochemical
reaction
in
which
serves
source.
Unlike
previous
reactions
involving
substrate,
exclusively
proceed
via
radical
mechanisms,
this
follows
S‐cation
pathway.
A
wide
range
N
‐methylsulfinyl
were
successfully
obtained.
Deuterated
compounds
have
broad
applications
across
various
fields,
with
dehalogenative
deuteration
serving
as
an
efficient
method
to
obtain
these
molecules.
However,
the
diverse
electronic
structures
of
active
sites
in
heterogeneous
system
and
limited
recyclability
homogeneous
significantly
hinder
advancement
deuteration.
In
this
study,
we
present
a
catalyst
composed
copper
single-atom
anchored
within
ordered
mesoporous
nitrogen-doped
carbon
matrix,
synthesized
via
mesopore
confinement
method.
The
Cu1/OMNC-1100
catalyst,
characterized
by
Cu-N4
sites,
demonstrates
exceptional
performance,
high
functional
group
tolerance,
remarkable
durability
2-bromo-6-methoxynaphthalene
under
relatively
mild
conditions
(80
°C,
2
MPa
CO).
Experimental
results
combined
X-ray
absorption
fine
structure
analysis
reveal
that
Cu-N3
can
be
converted
into
more
stable
counterparts
at
higher
pyrolysis
temperatures,
resulting
enhanced
catalytic
activity.
This
work
strategy
for
designing
site
catalysts
tunable
coordination
environments,
providing
promising
approach
improving
performance
selective
reactions
conditions.
Abstract
The
electrochemical
catalyst‐free
generation
of
carbon
radicals
bearing
three
electron‐withdrawing
groups
from
the
corresponding
C−H
nucleophiles
remains
unexplored.
To
this
end,
we
report
a
direct
electro‐oxidation
strategy
to
access
these
electrophilic
under
conditions.
Enabled
by
strategy,
radical
1,2‐alkylarylations
allylic
alcohols
was
realized,
affording
β
‐quaternary
ketones
with
high
functional
group
compatibility.
This
protocol
is
operationally
simple
and
also
easy
scale
up.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: March 10, 2025
Abstract
Deuterium
labeling
has
found
extensive
applications
across
various
research
fields,
including
organic
synthesis,
drug
design,
and
molecular
imaging.
Electrocatalytic
semi-hydrogenation
of
alkynes
offers
a
viable
route
for
the
synthesis
Z
-alkenes,
yet
it
falls
short
in
achieving
semi-deuteration
these
compounds.
In
this
study,
we
report
an
electrochemical
cobalt-catalyzed
transfer
deuteration
reaction
that
proficiently
accomplishes
alkynes,
yielding
-configuration
deuterated
alkene
products.
This
utilizes
cost-effective
cobalt
salts
as
catalysts
employs
D
2
O
AcOD
(acetic
acid-
d
)
economical
efficient
deuterium
sources,
underscoring
its
practicality
feasibility.
The
demonstrates
broad
alkyne
substrate
scope,
high
efficiency,
good
functional
group
compatibility,
excellent
-selectivity,
remarkable
degree
rate.
