The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 25, 2025
The
direct
alkylation
of
carbonyl
compounds
at
α
&
β
positions
represents
a
significant
challenge.
Here,
we
report
catalyst-free
visible
light-induced
deaminative
that
efficiently
produces
α,
β-alkylated
malononitrile-assisted
ketones.
Mechanistic
studies
suggested
an
EDA
complex
is
formed
by
the
Katritzky
salt
and
carbanion
malononitrile-aided
ketones,
which
permits
disruption
C-N
bonds
generation
alkyl
radicals.
Remarkably,
this
strategy
eliminates
need
for
metal
catalysts,
additives,
ligands
offering
enhanced
environmental
sustainability
features
mild,
catalyst-free,
broad
functional
group
tolerance.
Our
optimized
condition
under
blue
LED
light
yielded
regio
isomers
ketones
in
good
to
excellent
yields
with
diverse
electronic
properties
substitutions.
Implementation
flow
setup
batch
protocol
efficiency
reaction,
demonstrating
robustness
organic
synthesis.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(4), С. 2583 - 2592
Опубликована: Янв. 17, 2024
Catalytic
electron
donor–acceptor
(EDA)
complexes
have
recently
emerged
as
a
powerful
and
sustainable
alternative
to
iridium-
ruthenium-based
photoredox
synthetic
methods.
Yet,
these
remain
underexplored
reliant
on
the
use
of
meticulously
designed
acceptors
that
require
previous
installation.
Herein,
we
report
novel
EDA
complex
employing
tris(4-methoxyphenyl)
amine
catalytic
donor
for
sulfonylation
alkenes
using
inexpensive
readily
available
sulfonyl
chlorides.
Applying
this
operationally
simple,
visible-light-mediated
general
platform,
both
redox-neutral
net-reductive
functionalization
more
than
60
substrates,
encompassing
vinylic
or
allylic
sulfonylation,
hydrosulfonylation,
sulfamoylation
activated
unactivated
alkynes.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(16)
Опубликована: Янв. 29, 2024
Abstract
We
highlight
key
contributions
in
the
field
of
direct
radical
C
Ar
−
H
(hetero)aromatic
functionalization
involving
fluorinated
radicals.
A
compilation
Functional
Group
Transfer
Reagents
and
their
diverse
activation
mechanisms
leading
to
release
radicals
are
discussed.
The
substrate
scope
for
each
is
analyzed
classified
into
three
categories
according
electronic
properties
substrates.
Density
functional
theory
computational
analysis
provides
insights
chemical
reactivity
several
through
electrophilicity
nucleophilicity
parameters.
Theoretical
reduction
potentials
also
highlights
remarkable
correlation
between
oxidizing
ability.
It
established
that
highly
(e.g.
⋅OCF
3
)
capable
engaging
single‐electron
transfer
(SET)
processes
rather
than
addition,
which
good
agreement
with
experimental
literature
data.
scale,
based
on
barrier
addition
these
benzene
elaborated
using
high
accuracy
DLPNO‐(U)CCSD(T)
method.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Фев. 29, 2024
Abstract
The
photochemical
properties
of
Electron
Donor-Acceptor
(EDA)
complexes
present
exciting
opportunities
for
synthetic
chemistry.
However,
these
strategies
often
require
an
inert
atmosphere
to
maintain
high
efficiency.
Herein,
we
develop
EDA
complex
photocatalytic
system
through
rational
design,
which
overcomes
the
oxygen-sensitive
limitation
traditional
systems
and
enables
aerobic
oxygenation
reactions
dioxygen
activation.
mild
oxidation
transfers
electrons
from
donor
effective
catalytic
acceptor
upon
visible
light
irradiation,
are
subsequently
captured
by
molecular
oxygen
form
superoxide
radical
ion,
as
demonstrated
specific
fluorescent
probe,
dihydroethidine
(DHE).
Furthermore,
this
visible-light
mediated
oxidative
protocol
is
successfully
applied
in
boronic
acids.
We
believe
that
activation
strategy
enabled
not
only
provides
a
practical
approach
but
also
promotes
design
application
photocatalysis
under
ambient
conditions.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(10), С. 4926 - 4975
Опубликована: Янв. 1, 2024
In
search
for
the
perfect
wave(length).
This
review
is
dedicated
to
recent
efforts
in
development
of
visible
light
driven
photochemical
strategies
occurring
coloured
organic
compounds.
Green Chemistry,
Год журнала:
2024,
Номер
26(5), С. 2721 - 2729
Опубликована: Янв. 1, 2024
Herein,
we
report
a
mechanochemical-assisted
decarboxylative
sulfonylation
of
α,β-unsaturated
carboxylic
acids
with
sodium
sulfinate
salts
using
potassium
iodide
as
an
activator
under
water-assisted
grinding
conditions.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(17), С. 2818 - 2849
Опубликована: Июль 7, 2023
Abstract
In
the
last
fifteen
years,
development
of
visible‐light
photocatalysis,
metal/photoredox
dual
catalysis
has
become
forefront
as
a
new
paradigm
in
organic
synthesis
well
carbohydrate
chemistry.
It
led
to
discovery
unprecedented
transformations
and
also
improvement
known
reactions
under
mild
conditions,
employing
simple
household
light
sources
bench‐stable
precursors,
which
meet
requirements
green
chemistry
sustainable
excellent
yield
stereocontrol.
general
sense,
exploitation
photoredox
hinges
on
capability
photocatalyst
or
redox
mediator
transform
visible
into
chemical
energy
via
photo‐irradiated
SET
(single
electron
transfer),
PET
(photoinduced
HAT
(hydrogen
atom
XAT
(halogen
transfer)
potentially
unlock
unique
reaction
pathways,
thereby
generating
diverse
array
reactive
intermediates.
view
type,
mechanism,
status,
this
review
will
systematically
summarize
latest
advances
visible‐light‐promoted
photocatalytic
glycosylation
reactions,
are
driven
by
single
photoactivity
donor‐acceptor
(EDA)
complexes.
RSC Sustainability,
Год журнала:
2024,
Номер
2(8), С. 2169 - 2189
Опубликована: Янв. 1, 2024
This
review
describes
the
recent
advancements
in
visible
light-induced
bromine
radical
enhanced
hydrogen
atom
transfer
(HAT)
reactions
organic
synthesis.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(20), С. 5762 - 5768
Опубликована: Янв. 1, 2024
A
novel
catalyst-free
photoinduced
difluoromethylation–cyclization
via
electron
donor–acceptor
(EDA)
complexes
was
developed
for
the
synthesis
of
fluorinated
compounds.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(23), С. 4723 - 4743
Опубликована: Янв. 1, 2023
Vinyl
azides
have
emerged
as
highly
versatile
precursors
in
organic
synthesis
due
to
their
rich
reactivity
driven
by
the
excellent
leaving-group
ability
of
molecular
nitrogen.
Over
years,
significant
advancement
has
been
achieved
manipulation
vinyl
for
construction
C-C
and
C-X
bonds.
Typical
methods
involve
application
transition
metals
strong
oxidants
conversion
into
useful
compounds
employing
harsh
reaction
conditions
coupled
with
intense
product
purification.
In
this
regard,
visible
light
chemistry
become
one
most
exciting
fields
being
mild,
sustainable,
often
orthogonal
conventional
approaches.
Visible
light-induced
reactions
involving
generate
either
2H-azirines
or
iminyl
radicals
key
intermediates,
which
may
undergo
further
transformations
form
desired
cyclic
acyclic
products.
Herein,
we
provide
synthetic
transient
intermediates
biological
significance
under
photocatalysis.
We
classified
review
two
parts:
(i)
formation
an
radical
intermediate
(ii)
2H-azirine
intermediate-based
reactions.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(7), С. 1378 - 1385
Опубликована: Янв. 1, 2024
An
efficient
transition-metal/photocatalyst-free
visible-light-driven
one-pot
three-component
reaction
between
thianthrenium
salts,
carbon
disulfide
and
amines
under
air
atmosphere
for
the
preparation
of
S
-aryl
dithiocarbamates
is
developed.
