The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(24), С. 17037 - 17046
Опубликована: Ноя. 27, 2023
In
this
work,
we
present
the
CS2/KOH
system
as
a
practical
and
efficient
reductive
medium
for
obtaining
(E)-alkenes
from
alkynes
through
highly
stereoselective
semireduction
reaction.
This
cost-effective
enabled
successful
reactions
of
diverse
using
water
hydrogen
source,
yielding
moderate
to
excellent
yields.
The
versatility
protocol
is
further
demonstrated
synthesis
relevant
compounds
such
pinosylvin
resveratrol
precursors,
along
with
notable
anticancer
agent
DMU-212.
Furthermore,
during
reaction
scope
investigation,
serendipitously
disclosed
that
was
also
able
promote
Zinin-type
reduce
nitroarenes
into
arylamines.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(18), С. 9378 - 9418
Опубликована: Янв. 1, 2024
Organic
transformation
by
light-driven
catalysis,
especially,
photocatalysis
and
photothermal
denoted
as
photo(thermal)
is
an
efficient,
green,
economical
route
to
produce
value-added
compounds.
In
recent
years,
owing
their
diverse
structure
types,
tunable
pore
sizes,
abundant
active
sites,
metal-organic
framework
(MOF)-based
catalysis
has
attracted
broad
interest
in
organic
transformations.
this
review,
we
provide
a
comprehensive
systematic
overview
of
MOF-based
for
First,
the
general
mechanisms,
unique
advantages,
strategies
improve
performance
MOFs
are
discussed.
Then,
outstanding
examples
transformations
over
introduced
according
reaction
type.
addition,
several
representative
advanced
characterization
techniques
used
revealing
charge
kinetics
intermediates
presented.
Finally,
prospects
challenges
field
proposed.
This
review
aims
inspire
rational
design
development
materials
with
improved
catalysis.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(9)
Опубликована: Янв. 10, 2023
Prospects
in
light-driven
water
activation
have
prompted
rapid
progress
hydrogenation
reactions.
We
describe
a
Ni2+
-N4
site
built
on
carbon
nitride
for
catalyzed
semihydrogenation
of
alkynes,
with
supplying
protons,
powered
by
visible-light
irradiation.
Importantly,
the
photocatalytic
approach
developed
here
enabled
access
to
diverse
deuterated
alkenes
D2
O
excellent
deuterium
incorporation.
Under
irradiation,
evolution
four-coordinate
species
into
three-coordinate
Ni+
was
spectroscopically
identified.
In
combination
theoretical
calculations,
photo-evolved
is
posited
as
HO-Ni+
-N2
an
uncoordinated,
protonated
pyridinic
nitrogen,
formed
coupled
reduction
and
dissociation.
The
paired
Ni-N
prompts
hydrogen
liberation
from
water,
it
renders
desorption
alkene
preferred
over
further
alkane,
ensuring
selectivity.
The
chemo-
and
stereoselective
semi-hydrogenation
of
alkynes
to
alkenes
is
a
fundamental
transformation
in
synthetic
chemistry,
for
which
the
use
precious
4d
or
5d
metal
catalysts
well-established.
In
mankind's
unwavering
quest
sustainability,
research
focus
has
considerably
veered
towards
3d
metals.
Given
their
high
abundancy
availability
as
well
lower
toxicity
noxiousness,
they
are
undoubtedly
attractive
from
both
an
economic
environmental
perspective.
Herein,
we
wish
present
noteworthy
groundbreaking
examples
diastereoselective
alkyne
embark
on
journey
through
first-row
transition
Angewandte Chemie,
Год журнала:
2023,
Номер
135(9)
Опубликована: Янв. 10, 2023
Abstract
Prospects
in
light‐driven
water
activation
have
prompted
rapid
progress
hydrogenation
reactions.
We
describe
a
Ni
2+
−N
4
site
built
on
carbon
nitride
for
catalyzed
semihydrogenation
of
alkynes,
with
supplying
protons,
powered
by
visible‐light
irradiation.
Importantly,
the
photocatalytic
approach
developed
here
enabled
access
to
diverse
deuterated
alkenes
D
2
O
excellent
deuterium
incorporation.
Under
irradiation,
evolution
four‐coordinate
species
into
three‐coordinate
+
was
spectroscopically
identified.
In
combination
theoretical
calculations,
photo‐evolved
is
posited
as
HO−Ni
an
uncoordinated,
protonated
pyridinic
nitrogen,
formed
coupled
reduction
and
dissociation.
The
paired
Ni−N
prompts
hydrogen
liberation
from
water,
it
renders
desorption
alkene
preferred
over
further
alkane,
ensuring
selectivity.
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.
Abstract
Light‐powered
strategies
for
the
semi‐hydrogenation
of
acetylene
to
ethylene
are
rapidly
emerging
as
sustainable
alternatives
traditional
thermochemical
processes.
The
development
a
robust,
selective,
well
recyclable,
non‐noble
catalyst
that
can
be
powered
by
visible
light
and
uses
water
proton
source
accomplish
this
important
reaction
remains
key
challenge.
Here
first
demonstration
cobalt
single‐atom
supported
on
carbon‐nitride
(Co−CN)
an
all‐in‐one
photocatalyst
is
reported
using
source,
offering
advantages
over
current
hydrogenation
technologies.
Carbon
nitride
hosts
individual
catalytic
active
sites
thus
combining
photosensitizer
cocatalyst
in
one
unit,
line
with
first‐principles
modelling.
Under
irradiation,
Co−CN
reduces
stable
activity
40
days
continuous
operation,
≥99.9%
selectivity,
provides
means
coupling
organic
upgrading
produce
valuable
oxidation
products.
heterogeneous
easily
recovered
reused
repeatedly
without
loss
structural
integrity.
Thereby,
integrated
recyclable
platform
overcomes
need
separate
catalyst,
noble
metal
catalysts
external
H
2
gas
feed.
