The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 30, 2025
The
direct
cross-couplings
of
aryl
nonaflates
with
bromides
could
be
successfully
accomplished
by
utilizing
nickel
as
the
catalyst,
magnesium
metal
mediator,
and
lithium
chloride
additive.
reactions
proceeded
efficiently
in
THF
at
room
temperature
to
produce
desired
biaryls
moderate
good
yields,
showing
both
a
reasonable
substrate
scope
functional
group
tolerance.
Additionally,
an
equally
performance
realized
when
reaction
was
subjected
scale-up
synthesis.
Preliminary
study
suggested
that
presumably
proceeds
through
situ
formation
arylmagnesium
reagent
key
intermediate.
We
report
here
a
step-economic
and
cost-effective
cross-electrophile
coupling
of
aryl
thianthrenium
salts
with
widely
available
bromides,
which
proceeded
effectively
via
C-S
bond
activation
at
ambient
temperature
in
THF
the
presence
palladium
catalyst,
magnesium
turnings,
lithium
chloride
to
enable
facile
assembly
wide
array
structurally
diverse
biaryls
modest
good
yields
functional
group
compatibility.
In
addition,
gram-scale
reaction
could
also
be
realized.
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)
Chemistry - An Asian Journal,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 12, 2025
Abstract
This
review
discloses
nickel‐
and
cobalt‐catalyzed
coupling
reactions
that
allow
C−P
bond
formation.
Activation
of
C−halide
bonds
to
form
phosphonium,
pentavalent
phosphorus,
or
trivalent
phosphorous
compounds
has
been
reported
with
both
metals.
However,
the
conversion
C−O
((activated)
ethers,
carbonates,
acetates)
into
ones
only
described
Ni.
Similarly,
there
are
more
examples
C−Y
(Y=C,
S,
N,
B)
activations
catalyzed
by
Ni
than
Co.
Nevertheless,
cross‐dehydrogenative
reaction
between
a
P−H
reagent
C−H
often
cobalt
nickel.
In
addition,
for
metals,
electrolytic
photocatalytic
processes
have
shown
produce
variety
containing
molecules.
aims
provide
an
overview
potential
metals
formation
highlight
remaining
challenges.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 7, 2025
Comprehensive
Summary
Cross‐coupling
reactions
between
aryl
halides
and
thiolates
or
selenolates
typically
require
transition
metals,
photocatalysts,
strong
bases,
or/and
malodorous
thiols/selenols,
with
various
mechanisms
proposed.
This
study
aims
to
leverage
a
new
application
of
neutral
ChB
address
these
challenges
enable
very
simple
photoinduced
cross‐electrophile
C—S/Se
coupling
using
readily
available
chalcogen
electrophiles.
Mechanistic
investigations
have
revealed
the
important
role
in
facilitating
single
electron
transfer
processes,
thereby
enabling
generation
thiolates/selenolates
from
stable
electrophiles
α
‐aminoalkyl
radicals,
which
possess
capability
abstract
halogen
atoms
iodides.
Moreover,
provided
support
for
radical
nucleophilic
substitution
mechanism.
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
We
present
a
facile,
general
and
transition-metal-catalyst
free
electrochemical
allylation
of
unactivated
alkyl
halides.
Broad
substrate
scopes,
excellent
functional
group
tolerance
late-stage
functionalization
showcase
its
synthetic
utility.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 7, 2025
Herein
we
describe
a
comprehensive
study
of
ligand
effects
on
optoelectronic
properties
series
Ir(III)
catalysts
which
undergo
formally
spin-forbidden
excitation
using
low-energy
light.
We
demonstrate
that
electronic
and
steric
tuning
several
variables
can
be
explained
by
their
impact
the
HOMO
LUMO
energies
complex.
Density
functional
theory
calculations
catalysts'
adiabatic
triplet
agree
with
experimental
results
to
within
0.05
eV
average.
As
many
these
subtle
are
independent
each
other,
merger
them
in
single
complex
tends
have
an
additive
effect
thus
succeeded
developing
family
highly
oxidizing
iridium
photocatalysts
operate
excitation.
