Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 5, 2024
Abstract
We
report
the
photocatalytic
oxidation
of
α‐carbonyl
radicals
amides
or
esters
to
corresponding
carbocations
through
super
photoreductant
CBZ6
induced
redox‐neutral
photocatalysis.
The
are
formed
by
β‐addition
alkyl
generated
in
situ
fragmentation
N
‐hydroxyphthalimide
α,β‐unsaturated
and
esters.
This
method
enables
α‐nucleophilic
addition
hydroxyl
alkoxyl
without
any
prefunctionalization.
Science,
Год журнала:
2023,
Номер
381(6665), С. 1474 - 1479
Опубликована: Сен. 28, 2023
Nitrogen
scanning
in
aryl
fragments
is
a
valuable
aspect
of
the
drug
discovery
process,
but
current
strategies
require
time-intensive,
parallel,
bottom-up
synthesis
each
pyridyl
isomer
because
lack
direct
carbon-to-nitrogen
(C-to-N)
replacement
reactions.
We
report
site-directable
C-to-N
reaction
allowing
unified
access
to
various
pyridine
isomers
through
nitrene-internalization
process.
In
two-step,
one-pot
procedure,
azides
are
first
photochemically
converted
3
ACS Catalysis,
Год журнала:
2023,
Номер
13(24), С. 15991 - 16011
Опубликована: Ноя. 28, 2023
Carbon
dioxide
radical
anion
(CO2•–)
is
a
highly
reactive
nucleophilic
species
that
has
recently
emerged
in
organic
chemistry
as
strong
single
electron
donor
(reductant)
and
reactant
for
the
synthesis
of
carboxylic
acids.
In
general,
CO2•–
can
be
generated
by
either
direct
reduction
CO2
or
HAT
formate
salts.
Achievements
reactions
involving
have
been
witnessed
recent
years.
This
Review
summarizes
advances
highlighting
some
challenges
identifying
potential
areas
improvement,
which
may
offer
inspiration
future
studies.
Science,
Год журнала:
2023,
Номер
382(6675), С. 1165 - 1170
Опубликована: Дек. 7, 2023
Catalysts
that
distinguish
between
electronically
distinct
carbon-hydrogen
(C–H)
bonds
without
relying
on
steric
effects
or
directing
groups
are
challenging
to
design.
In
this
work,
cobalt
precatalysts
supported
by
N
-alkyl-imidazole–substituted
pyridine
dicarbene
(ACNC)
pincer
ligands
described
enable
undirected,
remote
borylation
of
fluoroaromatics
and
expansion
scope
include
electron-rich
arenes,
pyridines,
tri-
difluoromethoxylated
thereby
addressing
one
the
major
limitations
first-row
transition
metal
C–H
functionalization
catalysts.
Mechanistic
studies
established
a
kinetic
preference
for
bond
activation
at
meta
-position
despite
cobalt-aryl
complexes
resulting
from
ortho
being
thermodynamically
preferred.
Switchable
site
selectivity
in
as
function
boron
reagent
was
preliminarily
demonstrated
using
single
precatalyst.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(31)
Опубликована: Март 28, 2024
Abstract
Photoinduced
aryl
radical
generation
is
a
powerful
strategy
in
organic
synthesis
that
facilitates
the
formation
of
diverse
carbon‐carbon
and
carbon‐heteroatom
bonds.
The
synthetic
applications
photoinduced
complex
compounds,
including
natural
products,
physiologically
significant
molecules,
functional
materials,
have
received
immense
attention.
An
overview
current
developments
production
methods
their
uses
given
this
article.
A
generalized
idea
how
to
choose
reagents
approach
for
radicals
described,
along
with
techniques
associated
mechanistic
insights.
Overall,
article
offers
critical
assessment
results
as
well
selection
reaction
parameters
specific
context
cascades,
cross‐coupling
reactions,
functionalization,
selective
C−H
functionalization
substrates.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(29), С. 16150 - 16159
Опубликована: Июль 12, 2023
Palladium-catalyzed
C-N
bond
forming
reactions
are
a
key
tool
in
modern
synthetic
organic
chemistry.
Despite
advances
catalyst
design
enabling
the
use
of
variety
aryl
(pseudo)halides,
necessary
aniline
coupling
partner
is
often
synthesized
discrete
reduction
step
from
nitroarene.
An
ideal
sequence
would
avoid
necessity
this
while
maintaining
reliable
reactivity
palladium
catalysis.
Herein,
we
describe
how
reducing
conditions
enable
new
chemical
steps
and
well-studied
catalysts,
resulting
new,
useful
transformation:
reductive
arylation
nitroarenes
with
chloroarenes
to
form
diarylamines.
Mechanistic
experiments
suggest
that
under
conditions,
BrettPhos-palladium
complexes
catalyze
dual
Organic Letters,
Год журнала:
2023,
Номер
25(16), С. 2863 - 2867
Опубликована: Апрель 17, 2023
CBZ6,
a
redox-neutral
non-donor-acceptor-type
organo-photocatalyst,
presents
strong
reductive
potential
with
an
oxidative
of
-2.16
V
(vs
SCE).
It
can
work
as
photosensitizer
for
both
single-electron
transfer
and
triplet
energy
processes.
This
feature
enables
site-selective
control
in
the
intramolecular
hydroarylation
acrylamides.
Both
5-exo-trig
6-endo-trig
cyclization
products
could
be
prepared
regiospecfically
under
mild
conditions.
No
transition
metal,
halogen-containing
reagents,
or
additional
reductant
oxidant
is
involved.
process
provides
concise
environmentally
sustainable
access
to
series
oxindoles
dihydroquinolinones.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 9, 2025
This
study
explores
the
deoxygenation
of
pyridine
N-oxides
and
presents
a
one-step
photoredox
method
for
direct
synthesis
2-hydroxymethylated
pyridines
from
N-oxides.
Mechanism
studies
elucidate
role
catalyst
provide
evidence
possible
electron
transfer
process
formation
key
radicals.
A
range
derivatives,
particularly
2-hydroxymethyl-substituted
pyridines,
which
may
be
difficult
to
obtain,
can
synthesized
in
single
step.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 31, 2025
Electro-organic
reduction
reactions
are
canonically
carried
out
at
a
cathode
which
significant
negative
potential
is
applied.
Specifically,
carbon
electrodes,
aryl
bromides
and
chlorides
undergo
heterogeneous
in
organic
solvents
potentials
more
than
−2
V
vs
E0′
for
the
Fc/Fc+
couple
(Fc
=
ferrocene).
To
decrease
overpotential
reactions,
homogeneous
or
electrocatalysis
strategies
often
employed.
Here,
we
present
an
electrochemical
method
to
reduce
that
initiated
by
oxidation
reaction
very
mild
(∼0
Fc/Fc+).
of
outer-sphere
redox
mediator,
1,1-dimethylferrocene,
dry
N,N-dimethylformamide
(DMF)
containing
oxalate
(C2O42–),
results
one-electron
C2O42–.
The
resulting
C2O4•–
decomposes
∼1
μs
release
dioxide
radical
anion
(CO2•–),
potent
reductant
oxidized
CO2
–2.68
Fc/Fc+.
In
this
way,
low
electrode
enables
chlorides,
otherwise
directly
reduced
potentials.
Using
method,
selective
hydrodehalogenations
electron-deficient
reticulated
vitreous
anode
with
up
quantitative
conversion
yields.
Cyclic
voltammetry
finite
difference
simulations
used
characterize
hydrodehalogenation
4-bromobenzonitrile
via
C2O42–
oxidation.
Additionally,
show
efficiency
tuned
deliberate
additions
water
DMF
solutions,
leading
substantial
improvement
overall
yields
without
interference
from
proton
reduction.