Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(23)
Опубликована: Апрель 4, 2024
Abstract
A
new
cross‐coupling
of
trifluoromethyl
arenes
has
been
realized
via
multiphoton
photoredox
catalysis.
Trifluoromethyl
were
demonstrated
to
undergo
selective
mono‐defluorinative
alkylation
under
mild
reaction
conditions
providing
access
a
series
valuable
α,α‐difluorobenzylic
compounds.
The
shows
broad
substrate
scope
and
general
functional
group
tolerance.
In
addition
the
electron‐deficient
that
are
easily
reduced
corresponding
radical
anion,
more
challenging
electron‐rich
substrates
also
successfully
applied.
Steady‐State
Stern‐Volmer
quenching
studies
indicated
by
excited
Ir‐based
photocatalyst.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(27)
Опубликована: Апрель 23, 2024
Homogeneous
electrocatalysts
can
indirect
oxidate
the
high
overpotential
substrates
through
single-electron
transfer
on
electrode
surface,
enabling
efficient
operation
of
organic
electrosynthesis
catalytic
cycles.
However,
problems
this
chemistry
still
exist
such
as
dosage,
difficult
recovery,
and
low
efficiency.
Single-atom
catalysts
(SACs)
exhibit
atom
utilization
excellent
activity,
hold
great
promise
in
addressing
limitations
homogeneous
catalysts.
In
view
this,
we
have
employed
Fe-SA@NC
an
advanced
redox
mediator
to
try
change
situation.
was
synthesized
using
encapsulation-pyrolysis
method,
it
demonstrated
remarkable
performance
a
range
reported
reactions,
construction
various
C-C/C-X
bonds.
Moreover,
potential
exploring
new
synthetic
method
for
electrosynthesis.
We
develop
electro-oxidative
ring-opening
transformation
cyclopropyl
amides.
reaction
system,
showed
good
tolerance
drug
molecules
with
complex
structures,
well
flow
electrochemical
syntheses
gram-scale
transformations.
This
work
highlights
SACs
electrosynthesis,
thereby
opening
avenue
chemistry.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 30, 2024
Abstract
Herein,
we
report
an
electroreduction
of
unactivated
alkyl
alkenes
enabled
by
[Fe]-H,
which
is
provided
through
the
combination
anodic
iron
salts
and
silane
generated
in
situ
via
cathodic
reduction,
using
H
2
O
as
H-source.
The
catalytic
amounts
Si-additive
work
H-carrier
from
to
generate
a
highly
active
species
under
continuous
electrochemical
conditions.
This
approach
shows
broad
substrate
scope
good
functional
group
compatibility.
In
addition
hydrogenation,
use
D
instead
provides
desired
deuterated
products
yields
with
excellent
D-incorporation
(up
>99%).
Further
late-stage
hydrogenation
complex
molecules
drug
derivatives
demonstrate
potential
application
pharmaceutical
industry.
Mechanistic
studies
are
performed
provide
support
for
proposed
mechanistic
pathway.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(44), С. 23910 - 23917
Опубликована: Окт. 26, 2023
The
merger
of
electrochemistry
and
transition
metal
catalysis
has
emerged
as
a
powerful
tool
to
join
two
electrophiles
in
an
enantioselective
manner.
However,
the
development
electroreductive
cross-couplings
olefins
remains
challenge.
Inspired
by
advantages
synergistic
use
with
nickel
catalysis,
we
present
here
Ni-catalyzed
cross-coupling
acrylates
aryl
halides
alkyl
bromides,
which
affords
chiral
α-aryl
carbonyls
good
excellent
enantioselectivity.
Additionally,
this
catalytic
reaction
can
be
applied
(hetero)aryl
chlorides,
is
difficult
achieve
other
methods.
combination
cyclic
voltammetry
analysis
electrode
potential
studies
suggests
that
NiI
species
activates
oxidative
addition
bromides
single-electron
transfer.
Organic Letters,
Год журнала:
2024,
Номер
26(2), С. 536 - 541
Опубликована: Янв. 5, 2024
In
the
presence
of
visible
light
irradiation,
organophoto/nickel
dual
catalysts,
and
mild
base
K2HPO4,
1,3-enynes
react
with
silanecarboxylic
acids
to
give
corresponding
α-silylallenes
high
selectivity.
this
uniquely
decarboxylative
hydrosilylation
1,3-enynes,
a
silyl
radical
process
is
involved
diverse
electron-rich
-poor
substrates
proceed
smoothly
in
moderate
excellent
yields.
This
transformation
particularly
synthetically
worthwhile
when
using
MeOD
as
solvent,
which
furnishes
new
access
α-silyldeuteroallenes.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(3)
Опубликована: Ноя. 13, 2023
Abstract
The
development
of
metal
complexes
that
function
as
both
photocatalyst
and
cross‐coupling
catalyst
remains
a
challenging
research
topic.
So
far,
progress
has
been
shown
in
palladium(0)
excited‐state
transition
catalysis
for
the
construction
carbon‐carbon
bonds
where
oxidative
addition
alkyl/aryl
halides
to
zero‐valent
palladium
(Pd
0
)
is
achievable
at
room
temperature.
In
contrast,
analogous
process
with
divalent
II
uphill
endothermic.
For
first
time,
we
report
can
act
light‐absorbing
species
undergoes
double
excitation
realize
carbon‐nitrogen
(C−N)
cross‐couplings
under
air.
Differently
substituted
aryl
be
applied
mild,
selective
amination
using
acetate
Density
functional
theory
studies
supported
by
mechanistic
investigations
provide
insight
into
reaction
mechanism.
ACS Catalysis,
Год журнала:
2024,
Номер
14(11), С. 8996 - 9007
Опубликована: Май 28, 2024
Three-component
reductive
dicarbofunctionalization
reactions
of
1,3-enynes
have
been
rarely
reported
because
the
intricate
control
chemo-
and
regioselectivity
required,
coupled
with
a
limited
understanding
radical
catalytic
species
involved.
Herein,
we
report
nickel-catalyzed
1,4-alkylarylation
method
for
to
yield
tri-
tetrasubstituted
allenes
using
readily
accessible
alkyl
aryl
iodides,
featuring
simple
operational
protocol
mild
reaction
conditions.
In
our
mechanistic
studies,
formation
propargyl/allenyl
was
substantiated
by
isolation
propargyl
dimer,
detection
corresponding
TEMPO–radical
adduct,
probe
experiments.
Two
reduced
L2NiAr
complexes,
expected
act
as
intermediates,
were
generated
characterized
EPR
spectroscopy
NiI
complexes.
The
stoichiometric
L2Ni(p-NCC6H4)
1,3-enyne
iodide
showed
conversion
into
dimer
allene,
suggesting
that
encompasses
same
key
steps
reaction,
i.e.,
activation
iodide,
generation
radical,
selective
coupling
this
component.
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.
