ACS Catalysis,
Год журнала:
2022,
Номер
12(22), С. 14337 - 14346
Опубликована: Ноя. 7, 2022
Fluorine-containing
molecules
are
central
motifs
in
pharmaceuticals,
agrochemicals,
and
functional
materials
owing
to
the
unique
properties
engendered
by
carbon–fluorine
bonds.
However,
chemoselective
synthesis
of
multifluorinated
biaryls,
a
motif
extensively
exploited
drug
discovery,
is
challenging
because
difficulty
controlling
selective
fluorination.
Herein,
we
report
site-selective
arylation
C–F
bonds
polyfluoroarenes
enabled
ruthenium
catalyst
system.
The
present
bond
proceeds
exclusively
at
ortho-position
polyfluorinated
arenes
through
ruthenium(0)
chelation
readily
modifiable
directing
group.
A
variety
broadly
available
organoboranes
applicable
this
functionalization,
furnishing
biaryls
featuring
removable
aldehyde
handle.
Notably,
conditions
enable
programmed
integrated
C–F/C–H
functionalization
same
catalyst.
This
approach
characterized
broad
scope
group
tolerance
build
complex
biaryls.
synthetic
utility
highlighted
ligands,
heterocycles,
porphyrin
analogues.
DFT
studies
provide
insight
into
key
selectivity
activation.
We
fully
expect
that
will
facilitate
implementation
defluorination
utilizing
with
high
fluorine
content.
Chemical Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 26, 2024
Cross-electrophile
coupling
(XEC),
defined
by
us
as
the
cross-coupling
of
two
different
σ-electrophiles
that
is
driven
catalyst
reduction,
has
seen
rapid
progression
in
recent
years.
As
such,
this
review
aims
to
summarize
field
from
its
beginnings
up
until
mid-2023
and
provide
comprehensive
coverage
on
synthetic
methods
current
state
mechanistic
understanding.
Chapters
are
split
type
bond
formed,
which
include
C(sp
Organic Letters,
Год журнала:
2023,
Номер
25(10), С. 1771 - 1775
Опубликована: Март 2, 2023
A
straightforward
cross-coupling
of
aryl
thioether
with
bromide
the
aid
nickel
salt,
magnesium,
and
lithium
chloride
in
tetrahydrofuran
at
ambient
temperature
was
accomplished.
The
one-pot
reactions
proceeded
efficiently
via
C-S
bond
cleavage
to
produce
desired
biaryls
modest
good
yields,
avoiding
use
pregenerated
or
commercial
organometallic
reagents.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(20), С. 5171 - 5179
Опубликована: Янв. 1, 2023
We
report
a
cross-electrophile
coupling
of
aryl
thiols
with
bromides
via
C–S
bond
activation
instead
S–H
cleavage.
The
reaction
proceeded
effectively
in
the
presence
nickel
catalyst,
magnesium,
and
lithium
chloride
to
afford
various
biaryls
moderate
good
yields.
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.
ACS Catalysis,
Год журнала:
2021,
Номер
11(21), С. 12915 - 12930
Опубликована: Окт. 8, 2021
C–F
bond
activation
is
currently
considered
to
be
"a
hot
topic"
in
many
different
but
interconnected
fields
of
research,
due
its
inherent
inertness
and
unique
properties.
While
considerable
progress
has
been
made
this
particular
field
activating
strong
bonds,
such
as
the
bond,
continues
a
challenge.
Because
polyfluorinated
compounds
are
commercially
available,
functionalization
bonds
extensively
studied
for
preparing
partially
fluorinated
compounds,
some
which
biologically
active
used
functionalized
materials.
However,
chemo-
regioselective
methods
still
required
prepare
useful
compounds.
In
addition,
new
strategy
less
reactive
monofluorinated
remains
need.
Directed
strategies
have
C–H
chemistry
achieve
high
efficiency
well
regioselectivity.
On
other
hand,
directed
that
applicable
various
unreactive
C–O,
C–N,
C–F,
others
needed,
compared
with
activation.
Review,
we
focus
on
inert
bonds.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(51), С. 21484 - 21491
Опубликована: Дек. 17, 2021
Despite
their
importance
to
medicine
and
materials
science,
the
synthesis
of
biheteroaryls
by
cross-coupling
remains
challenging.
We
describe
here
a
new,
general
approach
biheteroaryls:
Ni-
Pd-catalyzed
multimetallic
cross-Ullmann
coupling
heteroaryl
halides
with
triflates.
An
array
5-membered,
6-membered,
fused
bromides
chlorides,
as
well
aryl
triflates
derived
from
heterocyclic
phenols,
proved
be
viable
substrates
in
this
reaction
(62
examples,
63
±
17%
average
yield).
The
generality
was
further
demonstrated
96-well
plate
format
at
10
μmol
scale.
96
possible
products
provided
>90%
hit
rate
under
single
set
conditions.
Further,
low-yielding
combinations
could
rapidly
optimized
"Toolbox
Plate"
ligands,
additives,
reductants.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(46), С. 24659 - 24667
Опубликована: Сен. 1, 2021
The
Ni-catalysed
cross-coupling
of
aryl
ethers
is
a
powerful
method
to
forge
new
C-C
and
C-heteroatom
bonds.
However,
the
inert
C(sp2
)-O
bond
means
that
canonical
mechanism
relies
on
oxidative
addition
ether
Ni0
centre
thermodynamically
kinetically
unfavourable,
which
suggests
alternative
mechanisms
may
be
involved.
Here,
we
provide
spectroscopic
structural
insights
into
anionic
pathway,
formation
electron-rich
hetero-bimetallic
nickelates
by
adding
organometallic
nucleophiles
centre.
Assessing
rich
co-complexation
chemistry
between
Ni(COD)2
PhLi
has
led
structures
solution-state
diverse
family
catalytically
competent
lithium
being
unveiled.
In
addition,
demonstrate
dramatic
solvent
donor
effects,
suggest
cooperative
activation
substrate
-ate
complexes
plays
key
role
in
catalytic
cycle.
ACS Catalysis,
Год журнала:
2021,
Номер
11(20), С. 12785 - 12793
Опубликована: Окт. 6, 2021
We
report
a
nickel-catalyzed
cross-electrophile
coupling
reaction
of
aryl
chlorides
and
heteroaryl
enabled
by
synergistic
combination
consisting
halide
effects
the
addition
magnesium
salt.
The
relies
on
electronic
difference
between
aromatic
heteroaromatic
partners
to
afford
cross-coupled
biaryl
products
using
single
catalyst.
A
variety
heterocycles
were
amenable
reaction,
as
well
wide
range
chlorides,
with
electron-deficient
performing
best
in
reaction.
Preliminary
mechanistic
evidence
demonstrates
MgCl2
is
essential
accelerating
reduction
Ni(II),
that
small
quantities
iodide
lead
improved
yields.
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
41(24), С. 3539 - 3546
Опубликована: Авг. 19, 2023
Comprehensive
Summary
Cross‐electrophile
coupling
of
triazine
esters
with
aryl
bromides
could
be
facilely
accomplished
by
employing
nickel
as
catalyst,
magnesium
metal
mediator,
and
lithium
chloride
additive.
The
reactions
proceeded
efficiently
in
THF
at
room
temperature
through
C—O
bond
activation
to
afford
an
array
structurally
different
diaryl
ketones
moderate
good
yields
wide
functional
group
tolerance.
Control
experiments
showed
that
nickel,
magnesium,
chloride,
are
all
indispensable
for
the
performance
reaction.
Preliminary
mechanistic
exploration
indicated
situ
formed
arylmagnesium
reagent
insertion
into
bromide
might
serve
key
intermediate
cross‐coupling.
method
which
avoids
utilization
moisture‐labile
relatively
difficult‐to‐obtain
organometallics
is
step‐economical,
cost‐efficient,
operationally
simple,
potentially
serving
attractive
alternative
documented
methods.
