Royal Society of Chemistry eBooks,
Год журнала:
2024,
Номер
unknown, С. 73 - 92
Опубликована: Дек. 6, 2024
Due
to
the
global
demand
for
more
sustainable
chemical
production,
Ni-catalysis
has
attracted
significant
attention,
leading
discovery
of
a
plethora
powerful
synthetic
transformations.
However,
mechanisms
by
which
these
transformations
occur
are
still
shrouded
in
mystery
and
poorly
understood.
In
particular,
roles
that
Lewis
acids
can
undertake
often
complicate
mechanistic
picture.
Herein,
we
discuss
several
examples
demonstrate
beneficial,
detrimental,
effects
have
Ni-catalysis.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 12, 2025
Herein,
we
investigate
the
photoactivity
of
four
NiII
tolyl
chloride
complexes
supported
by
either
new
bidentate
[2.2]pyridinophane
(HN2)
ligand
or
traditional
4,4'-di-tert-butyl-2,2'-dipyridyl
(tBubpy)
ligand.
Despite
a
change
in
framework,
observe
similar
quantum
yields
for
photodegradation
all
complexes,
while
noting
changes
their
affinity
radical
side
reactivity
and
ability
to
stabilize
photogenerated
mononuclear
NiI
species.
Furthermore,
changing
from
an
ortho-tolyl
para-tolyl
group
affects
geometry
makes
Ni
center
more
susceptible
reactivity.
By
leveraging
newly
developed
HN2
ligand,
that
hinders
axial
interactions
with
center,
limit
Time-dependent
density
functional
theory
(TDDFT)
complete
active
space
self-consistent
field
(CASSCF)
calculations
predict
have
accessible
MLCTs
excite
electron
Ni-aryl
bonding
orbital
into
antibonding
orbital,
initiating
photolysis.
decreasing
this
energy
gap
stabilizing
tetrahedral
triplet
excited
state,
increase
photoexcitation.
Importantly,
characterize
species
using
X-band
EPR
spectroscopy
show
HN2-supported
do
not
undergo
deleterious
dimerization
tetramerization
observed
(bpy)NiICl
Overall,
study
provides
valuable
insight
how
steric
environment
around
its
demonstrates
such
is
unique
bipyridyl-supported
compounds.
Research Square (Research Square),
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 16, 2024
Abstract
Enantioselective
electrocatalysis
bears
unique
potential
for
the
sustainable
assembly
of
enantiomerically
enriched
molecules
1–7
.
This
approach
allows
electro-oxidative
C–H
activation
to
be
performed
paired
hydrogen
evolution
reaction
8,9
While
recent
progress
featured
scarce
transition
metals
with
limited
availability
10–17
,
we,
herein,
reveal
that
Earth-abundant
3d
transition-metal
nickel
is
characterized
by
performance,
while
having
high
natural
abundance
18
and
reduced
toxicity
19
Thereby,
electrocatalytic
enabled
enantioselective
desymmetrizations
bicyclic
alkenes,
leading
three-dimensional
molecular
building
blocks
multiple
stereogenic
elements
20
Here,
ligand
optimization
was
guided
smart
feature
analysis
enantioselectivity
enhancement.
The
detailed
mechanistic
investigation
experimental
studies
organometallic
intermediates
in
conjunction
computational
identified
key
features
design
including
non-covalent
interactions
21,22
guarantee
full
selectivity
control.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(9), С. 2512 - 2517
Опубликована: Янв. 1, 2024
A
Rh(
iii
)-catalysed
cascade
C–H
functionalization/[3
+
2]
dipolar
cycloaddition
was
realized
to
deliver
gem
-difluorinated
pentacyclic
indenopyrazolopyrazolones
with
four
continuous
chiral
carbon
centres
in
a
one-pot
fashion.
Great
advances
have
been
made
by
leveraging
high-valent
Pd(II)/Pd(IV)
catalysis
in
the
areas
of
C–H
activation
and
alkene
difunctionalisation,
thus
representing
a
powerful
approach
for
construction
carbon-carbon
carbon-heteroatom
bond.
However,
catalytic
reactions
involving
Ni(II)/Ni(IV)
are
largely
underdeveloped.
Here
we
report
Ni(II)-catalysed
dicarbofunctionalisation
unactivated
alkenes
via
catalysis.
This
protocol
provides
highly
efficient
direct
route
towards
vicinal
substituted
alkanes
using
primary,
secondary,
tertiary
amides,
as
well
secondary
amines
native
directing
group
under
redox-neutral
conditions
that
challenging
to
access
through
conventional
methods.
The
key
success
this
reaction
is
use
bulky
β-diketone
ligand,
which
could
enable
insertion
aryl-Ni(II)
species,
stabilize
alkyl-Ni(II)
species
inhibit
homolytic
cleavage.
features
group,
broad
substrate
scope,
excellent
scalability.
resulting
Weinreb
amide-derived
products
can
be
readily
derivatized
variety
ketones
aldehyde,
fundamentally
useful
synthetic
chemistry.
In
addition,
has
employed
preparation
several
bioactive
compounds,
showcasing
significant
values
our
current
method.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(13), С. 2926 - 2932
Опубликована: Май 15, 2024
Abstract
An
intermolecular
annulation
reaction
of
2‐aryl‐1,3‐indandions
with
alkynes
was
reported
using
Pd(OAc)
2
to
access
spirobi[indene]‐1,3‐diones.
Under
palladium
catalysis,
the
substrates
form
a
homocoupling
dimer
intermediate
through
catalytic
dehydrogenative
cross‐coupling
process.
The
palladium(II)
species
could
come
from
or
2‐aryl‐1,3‐indandion.
Notably,
this
pathway
is
not
typically
observed
in
enol‐directed
formal
sp
3
C−H
functionalization/oxidative
chemistry.
This
transformation
provides
route
class
functionalized
spiro
carbocyclic
indenes.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 28, 2024
Abstract
An
efficient
method
has
been
developed
for
the
preparation
of
1,4‐naphthoquinones
via
a
palladium‐catalyzed
reaction
2‐aryl‐1,3‐indandiones
with
olefins.
This
involves
tertiary
C−H
alkylation
olefins
to
produce
alcohol,
followed
by
C−C
bond
cleavage.
Royal Society of Chemistry eBooks,
Год журнала:
2024,
Номер
unknown, С. 73 - 92
Опубликована: Дек. 6, 2024
Due
to
the
global
demand
for
more
sustainable
chemical
production,
Ni-catalysis
has
attracted
significant
attention,
leading
discovery
of
a
plethora
powerful
synthetic
transformations.
However,
mechanisms
by
which
these
transformations
occur
are
still
shrouded
in
mystery
and
poorly
understood.
In
particular,
roles
that
Lewis
acids
can
undertake
often
complicate
mechanistic
picture.
Herein,
we
discuss
several
examples
demonstrate
beneficial,
detrimental,
effects
have
Ni-catalysis.
