The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(6), С. 4145 - 4155
Опубликована: Фев. 28, 2024
The
environmental
benefits
of
molecular
oxygen
as
the
oxidizing
agent
in
oxidation
reactions
that
synthesize
fine
chemicals
cannot
be
overstated.
Increased
interest
developing
robust
photocatalysts
is
stimulated
by
fact
current
photocatalytic
transformation
boom
has
made
previously
inaccessible
synthetic
approaches
possible.
Motivated
enzymatic
catalysis,
employing
a
reusable
phenalenyl-based
photocatalyst,
we
have
successfully
developed
oxidative
dehydrogenation
utilizing
greener
oxidant.
Under
photoinduced
conditions,
different
types
saturated
N-heterocycles
and
alcohols
were
dehydrogenated.
versatility
this
bioinspired
protocol
demonstrated
wide
variety
N-heteroaromatics,
such
quinoline,
carbazole,
quinoxaline,
acridine,
indole
derivatives,
well
aldehydes
ketones,
synthesized.
Detailed
mechanistic
studies
validate
proposed
mechanism.
Fluorescence
lifetime
CV
experiments
revealed
crucial
role
water
on
efficiency
reaction.
present
also
provides
chemoselectivity
scalability,
leading
to
superior
results
allowing
for
functionalization
bioactive
molecules
at
late
stage
sustainable
manner.
Chemical Science,
Год журнала:
2024,
Номер
15(29), С. 11418 - 11427
Опубликована: Янв. 1, 2024
An
environmentally
friendly
electroreduction
approach
is
disclosed
for
site-specific
introduction
of
deuterium
via
anti-Markovnikov
selective
deuteroarylation
alkenes
and
aryl
iodides
with
bipyridine
as
a
mediator
D
2
O
‘D’
source.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 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,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 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.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(17), С. 2049 - 2055
Опубликована: Май 7, 2024
Comprehensive
Summary
An
electrocatalytic
multicomponent
cascade
cross‐coupling
for
the
synthesis
of
chalcogenosulfonates
has
been
established.
This
approach
does
not
require
use
transition
metals,
acids,
and
external
oxidants.
The
gentle
conditions
tolerance
to
a
wide
variety
functional
groups
permit
derivatization
complex
indoles.
Beilstein Journal of Organic Chemistry,
Год журнала:
2024,
Номер
20, С. 2500 - 2566
Опубликована: Окт. 9, 2024
With
the
resurgence
of
electrosynthesis
in
organic
chemistry,
there
is
a
significant
increase
number
routes
available
for
late-stage
functionalization
(LSF)
drugs.
Electrosynthetic
methods,
which
obviate
need
hazardous
chemical
oxidants
or
reductants,
offer
unprecedented
control
reactions
through
continuous
variation
applied
potential
and
possibility
combination
with
photochemical
processes.
This
capability
substantial
advantage
performing
electrochemical
photoelectrochemical
LSF.
Ultimately,
these
protocols
are
poised
to
become
vital
component
medicinal
chemist's
toolkit.
In
this
review,
we
discuss
that
have
been
demonstrated
be
applicable
LSF
pharmaceutical
drugs,
their
derivatives,
natural
substrates.
We
present
analyze
representative
examples
illustrate
electrochemistry
photoelectrochemistry
valuable
molecular
scaffolds.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Ноя. 8, 2024
Aryl
thianthrenium
salts
are
valuable
in
photocatalysis
but
traditionally
require
external
electron
donors
for
activation.
This
study
introduces
an
energy
transfer
(EnT)
strategy
the
activation
of
aryl
using
2,3,4,5,6-penta(carbazol-9-yl)benzonitrile
(5CzBN)
as
a
metal-free
photocatalyst,
eliminating
need
donors.
Utilizing
this
EnT
approach,
we
achieve
C-H
deuteration
arenes
under
visible
light
with
CDCl
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)
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Март 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.
