Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(18)
Published: March 8, 2023
Abstract
Despite
the
advances
in
field
of
carbon‐halogen
bond
formation,
straightforward
catalytic
access
to
selectively
functionalized
iodoaryls
remains
a
challenge.
Here,
we
report
one‐pot
synthesis
ortho
‐iodobiaryls
from
aryl
iodides
and
bromides
by
palladium/norbornene
catalysis.
This
new
example
Catellani
reaction
features
initial
cleavage
C(sp
2
)−I
bond,
followed
key
formation
palladacycle
through
C−H
activation,
oxidative
addition
an
bromide
ultimate
restoration
bond.
A
large
variety
valuable
o
has
been
synthesized
satisfactory
good
yields
their
derivatization
have
described
too.
Beyond
synthetic
utility
this
transformation,
DFT
study
provides
insights
on
mechanism
reductive
elimination
step,
which
is
driven
original
transmetallation
between
palladium(II)‐halides
complexes.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(3), P. 1970 - 1975
Published: Jan. 22, 2024
A
nickel/blue
light-catalyzed
carbohalogenation
reaction
is
reported.
nickel
catalyst
and
an
inexpensive
phosphine
ligand
promote
the
of
aryl
iodides
bromides
with
π
systems
to
enable
construction
a
library
halogenated
heterocyclic
scaffolds.
Mechanistic
studies
provide
insight
regarding
fundamental
steps
catalytic
cycle,
including
reversible
C–X
bond
formation
via
deuterium
labeling
EPR
experiments,
while
preliminary
enantioselective
results
suggest
two-electron
migratory
insertion.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(31), P. 16750 - 16762
Published: March 1, 2021
Abstract
Nickel
catalysis
has
demonstrated
the
capability
of
performing
a
broad
range
synthetically
challenging
transformations
over
last
decade.
Though
recent
literature
focused
on
formation
C−C
and
C−N
bonds,
variety
breakthroughs
in
field
C−X
bond
generation
have
also
been
reported.
A
diverse
strategies
using
nickel
developed,
an
effort
to
expand
scope
synthetic
utility
these
halogenation
methods.
This
Minireview
will
cover
six
emerging
this
including:
oxidatively
induced
reductive
elimination,
triflate‐to‐halogen
exchange
reactions,
directed
C−H
halogenation,
non‐directed
electrophilic
arenes,
enantioselective
α‐fluorination
carbonyl
containing
compounds,
1,2‐difunctionalization‐halogenation
reactions.
The
final
section
split
into
two
parts:
nickel‐catalyzed
hydrohalogenation
carbohalogenation
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(20), P. 12785 - 12793
Published: Oct. 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.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(9)
Published: Dec. 16, 2022
A
flurry
of
recent
research
has
centered
on
harnessing
the
power
nickel
catalysis
in
organic
synthesis.
These
efforts
have
been
bolstered
by
contemporaneous
development
well-defined
(pre)catalysts
with
diverse
structure
and
reactivity.
In
this
report,
we
present
ten
different
bench-stable,
18-electron,
formally
zero-valent
nickel-olefin
complexes
that
are
competent
pre-catalysts
various
reactions.
Our
investigation
includes
preparations
novel,
bench-stable
Ni(COD)(L)
(COD=1,5-cyclooctadiene),
which
L=quinone,
cyclopentadienone,
thiophene-S-oxide,
fulvene.
Characterization
NMR,
IR,
single-crystal
X-ray
diffraction,
cyclic
voltammetry,
thermogravimetric
analysis,
natural
bond
orbital
analysis
sheds
light
structure,
bonding,
properties
these
complexes.
Applications
an
assortment
nickel-catalyzed
reactions
underscore
complementary
nature
within
toolkit.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(18)
Published: March 8, 2023
Abstract
Despite
the
advances
in
field
of
carbon‐halogen
bond
formation,
straightforward
catalytic
access
to
selectively
functionalized
iodoaryls
remains
a
challenge.
Here,
we
report
one‐pot
synthesis
ortho
‐iodobiaryls
from
aryl
iodides
and
bromides
by
palladium/norbornene
catalysis.
This
new
example
Catellani
reaction
features
initial
cleavage
C(sp
2
)−I
bond,
followed
key
formation
palladacycle
through
C−H
activation,
oxidative
addition
an
bromide
ultimate
restoration
bond.
A
large
variety
valuable
o
has
been
synthesized
satisfactory
good
yields
their
derivatization
have
described
too.
Beyond
synthetic
utility
this
transformation,
DFT
study
provides
insights
on
mechanism
reductive
elimination
step,
which
is
driven
original
transmetallation
between
palladium(II)‐halides
complexes.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(7), P. 2081 - 2087
Published: Jan. 1, 2024
A
Ni-catalyzed
C–S
coupling
has
been
proposed
based
on
mechanochemistry.
The
mechanochemical
synthesis
of
thioethers
is
realized
with
a
wide
range
disulfides
and
bromides.
multivalence
Ni-catalytic
cycle
for
bond
formation
proposed.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(27), P. 10352 - 10360
Published: June 23, 2021
The
direct
difunctionalization
of
alkenes
is
an
effective
way
to
construct
multiple
C-C
bonds
in
one-pot
using
a
single
functional
group.
regioselective
dicarbofunctionalization
therefore
important
area
research
rapidly
obtain
complex
organic
molecules.
Herein,
we
report
palladium-catalyzed
γ,γ'-diarylation
free
alkenyl
amines
through
interrupted
chain
walking
for
the
synthesis
Z-selective
amines.
Notably,
while
1,3-dicarbofunctionalization
allyl
groups
well
precedented,
present
disclosure
allows
highly
substituted
allylamines
give
trisubsubstituted
olefin
products.
This
cascade
reaction
operates
via
unprotected
amine-directed
Mizoroki-Heck
(MH)
pathway
featuring
β-hydride
elimination
selectively
walk
furnish
new
terminal
which
then
generates
cis-selective
around
sterically
crowded
moiety.
operationally
simple
protocol
applicable
variety
cyclic,
branched,
and
linear
secondary
tertiary
alkenylamines,
has
broad
substrate
scope
with
regard
arene
coupling
partner
as
well.
Mechanistic
studies
have
been
performed
help
elucidate
mechanism,
including
presence
likely
unproductive
side
C-H
activation
pathway.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(10), P. 6081 - 6091
Published: May 6, 2022
The
intramolecular
carbothiolation
of
unsaturated
hydrocarbons
using
a
palladium–NHC
catalyst
(NHC
=
N-heterocyclic
carbene)
is
described.
Herein,
single
system
enables
both
initial
activation
C(sp2)–S
bond
through
oxidative
addition
and
formation
C(sp3)–S
terminal
reductive
elimination,
unlocking
completely
atom-economical
transfer
across
alkenes.
reaction
tolerates
variety
different
functional
groups,
exhibits
excellent
chemoselectivity
in
the
presence
competing
thioether
moieties,
can
be
applied
to
various
alkenes
alkynes.
Furthermore,
product
derivatization
was
demonstrated
access
broad
sulfur-containing
compounds.
