Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(44)
Published: Sept. 14, 2023
Abstract
Herein,
an
electrochemically
driven
NiH‐catalyzed
reductive
coupling
of
alkyl
halides
and
alkenes
for
the
construction
C
sp
3
−C
bonds
is
firstly
reported.
Notably,
serve
dual
function
as
substrates
hydrogen
sources
to
generate
NiH
species
under
electrochemical
conditions.
The
tunable
nature
this
reaction
realized
by
introducing
intramolecular
coordinating
group
substrate,
where
product
can
be
easily
adjusted
give
desired
branched
products.
method
proceeds
mild
conditions,
exhibits
a
broad
substrate
scope,
affords
moderate
excellent
yields
with
over
70
examples,
including
late‐stage
modification
natural
products
drug
derivatives.
Mechanistic
insights
offer
evidence
process.
‐carbon‐halogen
activated
through
single
electron
transfer
(SET)
nickel
catalyst
in
its
low
valence
state,
generated
cathodic
reduction,
generation
from
pivotal
transformation.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(41), P. 7529 - 7534
Published: Oct. 11, 2023
The
electrochemical
synthesis
of
N-aroylsulfoximines
features
the
use
tetra-n-butylammonium
iodide
(TBAI)
as
medium
and
a
broad
substrate
scope,
thus
affording
wide
range
N-aroylated
sulfoximines
in
moderate
to
good
yields.
advantages
this
strategy
are
augmented
by
mild
reaction
conditions
that
external
oxidant-free,
ligand-free,
easy
scale
up
gram
scale.
Both
control
experiments
mechanistic
studies
revealed
whole
process
proceeded
through
palladium
(II/IV/II)
catalytic
cycle.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(23)
Published: April 22, 2024
Abstract
The
construction
of
carbonyl
compounds
via
carbonylation
reactions
using
safe
CO
sources
remains
a
long‐standing
challenge
to
synthetic
chemists.
Herein,
we
propose
catalyst
cascade
Scheme
in
which
2
is
used
as
surrogate
the
benzyl
chlorides.
Our
approach
based
on
cooperation
between
two
coexisting
catalytic
cycles:
‐to‐CO
electroreduction
cycle
promoted
by
[Fe(TPP)Cl]
(TPP=meso‐tetraphenylporphyrin)
and
an
electrochemical
catalyzed
[Ni(bpy)Br
]
(2,2′‐bipyridine).
As
proof
concept,
this
protocol
allows
for
synthesis
symmetric
ketones
from
good
excellent
yields
undivided
cell
with
non‐sacrificial
electrodes.
reaction
can
be
directly
scaled
up
gram‐scale
operates
effectively
at
concentration
10
%,
demonstrating
its
robustness.
mechanistic
studies
cyclic
voltammetry,
IR
spectroelectrochemistry
Density
Functional
Theory
calculations
suggest
synergistic
effect
catalysts.
produced
reduction
key
formation
[Ni(bpy)(CO)
],
proposed
intermediate
responsible
C−C
bond
steps.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 9, 2025
Direct
benzylic
C-H
carboxylation
stands
as
a
high
atom
economy,
efficient,
and
convenient
route
for
the
synthesis
of
valuable
carboxylic
acids,
which
are
great
significance
in
many
pharmaceuticals
bioactive
molecules.
However,
inherent
inertness
both
bonds
carbon
dioxide
presents
challenge
further
transformations.
Herein,
we
report
our
efforts
to
overcome
this
obstacle
via
halide-promoted
linear
paired
electrolysis
generate
various
acids.
Remarkably,
process
is
transition-metal-
base-free,
making
it
environmentally
benign
cost-effective.
Besides,
suitable
constructing
wide
range
primary,
secondary,
tertiary
acids
under
mild
reaction
conditions,
demonstrating
broad
substrate
scopes
good
functional
group
tolerance.
Furthermore,
protocol
enables
direct
some
drug
molecules,
including
Flurbiprofen,
Ibuprofen,
Naproxen,
facilitates
late-stage
modification
complex
compounds,
showcasing
practical
application
synthetic
chemistry
underscores
its
potential
advance
related
compounds.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 22, 2025
Palladium-catalyzed
bond-forming
reactions
such
as
carbonylations
offer
an
efficient
and
versatile
avenue
to
access
products
from
often
feedstock
reagents.
However,
the
use
of
catalysts
also
comes
with
a
cost,
their
need
be
regenerated
after
each
product-forming
cycle
requires
balancing
thermal
operations.
The
latter
can
lead
high
barriers
even
well
restrict
application
many
products.
We
introduce
herein
alternative
approach
palladium
catalyst
design,
where
instead
electrochemical
potential
drive
catalysis
by
continual
two-electron
cycling
metal
oxidation
state.
power
behind
these
redox
steps
offers
route
carry
out
carbonylation
reactions,
including
catalytic
synthesis
high-energy
aroyl
halide
electrophiles,
at
unprecedentedly
mild
ambient
temperature
pressure.
More
generally,
analysis
suggests
this
functions
distinct
multi-electron
exchange
pathway,
reduction
enables
oxidative
addition
drives
product
elimination.
combination
creates
unique
platform
both
reverse
operations
are
favored
in
same
system
energy
only
added
source.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(23), P. 5016 - 5020
Published: June 3, 2024
Spirolactones
are
widely
found
in
pharmaceuticals
and
bioactive
natural
products.
However,
efficient
environmentally
friendly
approaches
to
accessing
spirolactones
still
highly
desirable.
Herein,
a
novel
electrochemical
synthesis
of
from
α-tetralone
derivatives
with
methanol
as
C1
source
is
described.
This
reaction
exhibits
high
efficiency
good
functional
group
tolerance.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(12), P. 2430 - 2434
Published: March 19, 2024
A
highly
efficient
dehydrogenative
carbonylative
esterification
of
allenoic
acids
using
Pd-catalysis
was
developed,
providing
a
novel
approach
to
synthesizing
esterified
γ-butyrolactone
derivatives
with
consistently
good
excellent
results
demonstrated
across
over
50
examples.
Additionally,
we
used
heterogeneous
catalyst
known
as
Pd-AmP-MCF
and
harnessed
biomimetic-aerobic-oxidation
conditions
facilitate
the
practical
execution
this
reaction.
Furthermore,
our
detailed
study
products
highlighted
their
potential
in
bioactive
compounds.
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(45)
Published: Sept. 12, 2023
Abstract
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
(D
2
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.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(23)
Published: April 22, 2024
Abstract
The
construction
of
carbonyl
compounds
via
carbonylation
reactions
using
safe
CO
sources
remains
a
long‐standing
challenge
to
synthetic
chemists.
Herein,
we
propose
catalyst
cascade
Scheme
in
which
2
is
used
as
surrogate
the
benzyl
chlorides.
Our
approach
based
on
cooperation
between
two
coexisting
catalytic
cycles:
‐to‐CO
electroreduction
cycle
promoted
by
[Fe(TPP)Cl]
(TPP=meso‐tetraphenylporphyrin)
and
an
electrochemical
catalyzed
[Ni(bpy)Br
]
(2,2′‐bipyridine).
As
proof
concept,
this
protocol
allows
for
synthesis
symmetric
ketones
from
good
excellent
yields
undivided
cell
with
non‐sacrificial
electrodes.
reaction
can
be
directly
scaled
up
gram‐scale
operates
effectively
at
concentration
10
%,
demonstrating
its
robustness.
mechanistic
studies
cyclic
voltammetry,
IR
spectroelectrochemistry
Density
Functional
Theory
calculations
suggest
synergistic
effect
catalysts.
produced
reduction
key
formation
[Ni(bpy)(CO)
],
proposed
intermediate
responsible
C−C
bond
steps.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 12, 2024
A
rhodaelectro-catalyzed
double
dehydrogenative
Heck
reaction
of
indole-2-carboxylic
acids
with
alkenes
has
been
developed
for
the
synthesis
pyrano[3,4-
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(44)
Published: Sept. 14, 2023
Abstract
Herein,
an
electrochemically
driven
NiH‐catalyzed
reductive
coupling
of
alkyl
halides
and
alkenes
for
the
construction
C
sp
3
−C
bonds
is
firstly
reported.
Notably,
serve
dual
function
as
substrates
hydrogen
sources
to
generate
NiH
species
under
electrochemical
conditions.
The
tunable
nature
this
reaction
realized
by
introducing
intramolecular
coordinating
group
substrate,
where
product
can
be
easily
adjusted
give
desired
branched
products.
method
proceeds
mild
conditions,
exhibits
a
broad
substrate
scope,
affords
moderate
excellent
yields
with
over
70
examples,
including
late‐stage
modification
natural
products
drug
derivatives.
Mechanistic
insights
offer
evidence
process.
‐carbon‐halogen
activated
through
single
electron
transfer
(SET)
nickel
catalyst
in
its
low
valence
state,
generated
cathodic
reduction,
generation
from
pivotal
transformation.
