ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
15(1), P. 148 - 155
Published: Dec. 16, 2024
We
herein
describe
the
high-valent
cobalt-catalyzed
C(sp3)–H
functionalization
of
amide
derivatives
with
silver
acetylides
generated
in
situ.
The
reaction
proceeds
under
kinetic
control
at
60
°C,
a
catalyst
loading
5
mol
%.
These
extraordinarily
mild
conditions
for
Co-catalysis
enable
synthesis
5-(Z)-ethylidene
pyrrolidin-2-one
good
yield
and
selectivity.
Density
functional
theory
calculations
have
revealed
unique
mechanism
involving
Co–Ag
bimetallic
species,
rationalizing
nature
catalytically
active
species
role
each
additive.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(17), P. 10192 - 10280
Published: Aug. 8, 2024
Radical
C–H
functionalization
represents
a
useful
means
of
streamlining
synthetic
routes
by
avoiding
substrate
preactivation
and
allowing
access
to
target
molecules
in
fewer
steps.
The
first-row
transition
metals
(Ti,
V,
Cr,
Mn,
Fe,
Co,
Ni,
Cu)
are
Earth-abundant
can
be
employed
regulate
radical
functionalization.
use
such
is
desirable
because
the
diverse
interaction
modes
between
metal
complexes
species
including
addition
center,
ligand
complexes,
substitution
single-electron
transfer
radicals
hydrogen
atom
noncovalent
complexes.
Such
interactions
could
improve
reactivity,
diversity,
selectivity
transformations
allow
for
more
challenging
reactions.
This
review
examines
achievements
this
promising
area
over
past
decade,
with
focus
on
state-of-the-art
while
also
discussing
existing
limitations
enormous
potential
high-value
regulated
these
metals.
aim
provide
reader
detailed
account
strategies
mechanisms
associated
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(68), P. 8946 - 8977
Published: Jan. 1, 2024
Alkene
carbofunctionalization
reactions
have
great
potential
for
synthesizing
complex
molecules
and
constructing
structures
in
natural
products
medicinal
chemistry.
Recently,
dual
photoredox/nickel
catalysis
has
emerged
as
a
novel
strategy
alkene
carbofunctionalization.
Nickel
offers
numerous
advantages
over
other
transition
metals,
such
cost-effectiveness,
abundance,
low
toxicity,
moreover,
it
many
oxidation
states.
catalysts
exhibit
excellent
catalytic
activity
photoredox/transition
metal
catalysis,
facilitating
the
formation
of
carbon-carbon
or
carbon-heteroatom
bonds
organic
transformations.
This
review
highlights
latest
advancements
photoredox/nickel-catalyzed
carbofunctionalizations
includes
literature
published
from
2020
to
2024.
Asian Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
13(6)
Published: April 18, 2024
Abstract
Electron‐donor
acceptor
(EDA)
complex
has
been
an
integral
part
of
visible‐light
photocatalysis
and
is
different
from
the
traditional
photoredox
catalysis,
which
requires
exogenous
photocatalyst,
typically
a
colored
compound
to
initiate
photocatalytic
cycle.
Interestingly,
EDA‐complex
photochemistry
found
profound
use
in
activating
inert
α‐C−H
bonds
amines.
The
strategy
relied
upon
formation
between
donor
(amine)
(Lewis
acid),
harvesting
light
energy
perform
SET
process
generate
radical
cation
anion
intermediates.
then
loses
activated
acidic
proton
(because
SET,
acidity
α‐proton
increases
by
lowering
BDE)
form
α‐amino
radical,
participates
various
C−C
coupling
cascades.
In
this
review,
conceptual
approaches
for
generation
radicals
their
bond‐forming
reaction
under
triggered
will
be
discussed
with
particular
emphasis
on
mechanism
2018
onwards.
Chemical Society Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
This
review
provides
an
overview
of
the
research
advaces
in
Ni-,
Cu-,
Fe-
and
Co-catalyzed
directed
C(sp
3
)–H
bond
functionalization
reactions;
including
design
principles,
mechanistic
discussions,
along
with
potential
applications
limitations.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(22), P. 4390 - 4419
Published: Jan. 1, 2024
The
merger
of
organic
electrosynthesis
with
3d
transition-metal
catalysis
has
offered
huge
opportunities
for
modern
synthesis.
This
review
summarizes
the
key
advancements
in
this
direction
published
recent
two
years.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(13), P. 9666 - 9671
Published: June 15, 2024
A
cobalt
catalyst,
under
oxidative
conditions,
facilitates
the
single
electron
transfer
process
in
N-pyridyl
arylacetamides
to
form
α-carbon-centered
radicals
that
readily
react
with
molecular
oxygen,
giving
access
mandelic
acid
derivatives.
In
contrast
known
benzylic
hydroxylation
approaches,
this
approach
enables
chemo-
and
regioselective
at
a
position
adjacent
(N-pyridyl)amides.
Mild
broad
scope,
excellent
selectivity,
wide
synthetic
practicality
set
up
merit
of
reaction.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(13), P. 2554 - 2557
Published: Jan. 1, 2024
A
cobalt-catalyzed
ring
opening,
nucleophilic
amination
of
aziridines
and
azetidines
with
N
-fluorosulfonamides
has
been
established
toward
a
wide
range
1,2-
1,3-diamine
derivatives
in
moderate
to
good
yields
under
mild
conditions.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(35), P. 7302 - 7306
Published: Aug. 27, 2024
1-Isoindolinones
with
a
reactive
hydrazone
tether
attached
to
the
nitrogen
atom
underwent
an
intramolecular
alkylation
in
presence
of
cobalt(tetraphenylporphyrin)
and
base.
Products
display
saturated
heterocyclic
rings
various
sizes
(
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(14), P. 9352 - 9365
Published: June 29, 2023
The
merging
of
transition-metal-catalyzed
C–H
bond
activation
with
electro-oxidation
has
evolved
into
an
appealing
protocol
for
oxidative
functionalization.
Nevertheless,
specific
effects
the
process
on
reaction
mechanism
transition-metal
catalysis
have
rarely
been
investigated.
Herein,
we
present
a
comprehensive
computational
study
rhodium-catalyzed
electrochemical
phosphorylation
2-phenylpyridine
by
diphenylphosphine
oxide
to
reveal
mechanistic
details.
three
major
chemical
processes,
i.e.,
activation,
P–H
and
reductive
elimination/C–P
formation,
were
thoroughly
addressed
considering
steps
at
Rh(III),
Rh(IV),
Rh(V)
oxidation
states.
calculations
demonstrated
that
prefers
take
place
Rh(III)
state,
Rh(IV)
elimination
state.
Without
oxidation,
total
barrier
occurring
center
is
unsurmountable
under
experimental
temperature.
insights
disclosed
in
are
expected
be
beneficial
understanding
electro-oxidative
