The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 18, 2024
Using
amines
in
catalytic
transfer
hydrogenation
(TH)
is
challenging,
despite
their
potential
availability
as
a
hydrogen
source.
Here,
we
describe
photoredox/nickel-catalyzed
TH
of
alkyne
through
an
intermediary
aminoalkyl
Ni
species.
This
reaction
successfully
provided
functionalized
(Z)-alkenes,
such
(homo)allyl
ethers,
alcohols,
and
amides
(Z/E
=
up
to
>99:1),
the
thus
bypasses
limitation
substrate
scope
using
amine
Lindlar
catalyst.
Mechanistic
studies
revealed
that
species
plausibly
participates
two
catalyst
regeneration
paths:
(1)
β-hydride
elimination
followed
by
reductive
(2)
protodemetalation
from
alkenyl
NiI.
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 4665 - 4680
Опубликована: Март 5, 2025
Transition
metal
catalysis
is
an
indispensable
tool
for
organic
synthesis
that
has
been
harnessed,
modulated,
and
perfected
many
decades
by
careful
selection
of
centers
ligands,
giving
rise
to
synthetic
methods
with
unparalleled
efficiency
chemoselectivity.
Recent
developments
have
demonstrated
how
light
irradiation
can
also
be
recruited
as
a
powerful
dramatically
alter
the
outcome
catalytic
reactions,
providing
access
innovative
pathways
remarkable
potential.
In
this
context,
adoption
photochemical
conditions
mainstream
strategy
drive
reactions
unveiled
exciting
opportunities
exploit
rich
excited-state
framework
transition
metals
applications.
This
Perspective
examines
advances
in
application
complexes
standalone
photocatalysts,
exploiting
innate
reactivity
their
excited
states
beyond
common
use
photoredox
catalysts.
An
account
relevant
examples
dissected
provide
discussion
on
electronic
reorganization,
orbitals
involved,
associated
different
types
states.
analysis
aims
practitioners
fundamental
principles
guiding
strategies
understand,
design,
apply
light-activation
homogeneous
synthesis.
Bulletin of the Korean Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 25, 2024
Abstract
Paramagnetic
molecules,
such
as
main‐group
radicals
and
transition
metal
complexes,
play
crucial
roles
in
catalytic
enzymatic
reactions
organometallic
bioinorganic
chemistry.
Electron
paramagnetic
resonance
(EPR)
spectroscopy
emerges
a
powerful
tool
for
probing
the
intricate
electronic
geometric
structures
of
these
molecules.
The
application
EPR
spans
wide
spectrum
chemical
entities,
from
simple
to
metalloproteins,
clusters,
emphasizing
its
versatility
across
various
fields
This
review
introduces
spectra
offering
comprehensive
theoretical
foundation
along
with
illustrative
examples
both
These
highlight
effectiveness
characterizing
reinforcing
our
understanding
their
structure
reactivity.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(20), С. 5685 - 5694
Опубликована: Янв. 1, 2024
The
first
allenylic
alkylation
with
non-activated
aliphatic
amine
derivatives,
Katritzky
salts,
has
been
developed
via
photoredox/nickel
dual-catalyzed
reductive
deaminative
cross-electrophile
coupling.
This
study
presents
a
Ni-photoredox
method
for
indole
N-arylation,
broadening
the
range
of
substrates
to
include
indoles
with
unprotected
C3-positions
and
base-sensitive
groups.
Through
detailed
mechanistic
inquiries,
Ni(I/III)
mechanism
was
uncovered,
distinct
from
those
commonly
proposed
Ni-catalyzed
amine,
thiol,
alcohol
arylation,
as
well
Ni(0/II/III)
cycle
identified
amide
arylation
under
almost
identical
conditions.
The
key
finding
is
formation
Ni(I)
intermediate
bearing
nucleophile
ligand
prior
oxidative
addition,
which
rare
carbon-heteroatom
coupling
has
profound
impact
on
reaction
kinetics
scope.
pre-coordination
renders
more
electron-rich
intermediate,
broadens
scope
by
enabling
fast
reactivity
even
challenging
aryl
bromide
substrates.
Thus,
this
work
highlights
often-overlooked
influence
X-type
ligands
Ni
addition
rates
illustrates
yet
another
divergence
in
C–heteroatom
couplings.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 27, 2024
Abstract
This
study
presents
a
Ni‐photoredox
method
for
indole
N
‐arylation,
broadening
the
range
of
substrates
to
include
indoles
with
unprotected
C3‐positions
and
base‐sensitive
groups.
Through
detailed
mechanistic
inquiries,
Ni(I/III)
mechanism
was
uncovered,
distinct
from
those
commonly
proposed
Ni‐catalyzed
amine,
thiol,
alcohol
arylation,
as
well
Ni(0/II/III)
cycle
identified
amide
arylation
under
almost
identical
conditions.
The
key
finding
is
formation
Ni(I)
intermediate
bearing
nucleophile
ligand
prior
oxidative
addition,
which
rare
carbon‐heteroatom
coupling
has
profound
impact
on
reaction
kinetics
scope.
pre‐coordination
renders
more
electron‐rich
intermediate,
broadens
scope
by
enabling
fast
reactivity
even
challenging
aryl
bromide
substrates.
Thus,
this
work
highlights
often‐overlooked
influence
X‐type
ligands
Ni
addition
rates
illustrates
yet
another
divergence
in
C‐heteroatom
couplings.
Organic Letters,
Год журнала:
2024,
Номер
26(31), С. 6782 - 6786
Опубликована: Июль 31, 2024
Herein
we
report
a
photoredox/nickel-catalyzed
cross-coupling
of
aryl
bromides
with
1,1,1,3,3,3-hexafluoroisopropanol
for
the
construction
hexafluoroisopropyl
ethers.
The
mild
reaction
conditions
employed
allow
applicability
wide
range
and
heteroaryl
bromides.
Late-stage
functionalization
preliminary
mechanistic
studies
have
been
demonstrated.
Inorganic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 16, 2024
There
is
growing
demand
for
the
utilization
of
first-row
transition
metal
complexes
in
light-driven
processes
instead
their
conventional
noble
counterparts
due
to
greater
sustainability
complexes.
However,
major
drawback
ultrafast
lifetime
electronic
excited
states
these
complexes,
particularly
those
d
