Abstract
Cyanofunctionalization
of
alkenes
via
radical‐initiated
cyano
migration
was
a
straightforward
pathway
to
access
alkyl
nitriles.
Herein,
By
the
synergistic
merger
photoredox
catalysis
and
Brønsted
base
catalysis,
mild
protocol
alkylcyanation
unactivated
with
protic
C(sp
3
)−H
feedstocks
intramolecular
1,4‐cyano
group
reported.
This
method
enabled
in
an
atom‐,
step‐economy
manner,
delivering
series
γ‐cyanoester
derivatives
moderate
excellent
yields.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(9), С. 957 - 962
Опубликована: Янв. 18, 2024
Comprehensive
Summary
Multicomponent
alkene
1,2‐dicarbofunctionalizations
(DCFs)
have
emerged
as
a
powerful
strategy
to
rapidly
incorporate
both
two
carbon
subunits
across
one
C—C
double
bond
in
step
for
enhancing
molecular
complexity
and
diversity.
To
the
best
of
our
knowledge,
there
is
only
report
on
photoredox‐catalyzed
three‐component
DCFs
with
malonates
through
radical−radical
cross‐coupling,
while
radical‐polar
crossover
(RPC)‐type
were
still
rare.
Herein,
we
describe
redox‐neutral
RPC‐type
1,2‐dialkylation
styrenes
aldehydes
synergistic
Brønsted
base/photoredox
catalysis
system.
This
transition‐metal‐free
provides
an
efficient
clean
approach
broad
variety
δ‐hydroxy
esters
also
features
exceptionally
mild
conditions,
wide
compatibility
substrate
scope
functional
groups,
high
atomic
economy.
Moreover,
1,2‐alkylacylation
from
same
starting
materials
was
achieved
one‐pot
manner
such
coupling
subsequent
two‐electron
oxidation
process,
providing
set
δ‐keto
interest
pharmaceutical
research.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(62)
Опубликована: Авг. 10, 2024
The
difunctionalization
of
alkenes
represents
a
powerful
tool
to
incorporate
two
functional
groups
into
the
alkene
bones
for
increasing
molecular
complexity
and
has
been
widely
utilizations
in
chemical
synthesis.
Upon
catalysis
green,
sustainable,
mild
photo-/electrochemistry
technologies,
much
attentions
have
attracted
development
new
tactics
transformations
important
alkane
feedstocks
driven
by
C-H
radical
functionalization.
Herein,
we
summarize
recent
advances
photo-/electrocatalytic
enabled
We
detailedly
discuss
substrate
scope
mechanisms
reactions
selecting
impressive
synthetic
examples,
which
are
divided
four
sections
based
on
final
terminated
step,
including
oxidative
radical-polar
crossover
coupling,
reductive
radical-radical
transition-metal-catalyzed
coupling.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(51)
Опубликована: Июнь 27, 2023
Described
herein
is
a
visible-light
photoredox-catalyzed
regioselective
1,4-hydroalkylation
of
1,3-enynes.
Various
di-
and
tri-substituent
allenes
were
really
accessible
under
the
present
reaction
conditions.
The
photoredox
activation
carbon
nucleophile
to
generate
its
radical
species,
allowing
addition
with
un-activated
enynes.
synthetic
utility
for
protocol
was
demonstrated
by
large-scale
reaction,
as
well
derivatization
allene
product.
Radical-initiated
functionalization
of
bicyclo[1.1.0]butanes
(BCBs)
is
a
straightforward
approach
to
accessing
diverse
cyclobutane
derivatives.
However,
selective
C(sp3)–H
at
the
C2
position
BCBs
remains
scarce.
Herein,
mild
protocol
for
hydrogen-evolution
phosphorylation
with
enabled
by
photoinduced
cobaloxime
catalysis
was
realized
in
regio-
and
diastereoselective
manner.
This
oxidant-
additional
photocatalyst-free
method
wide
range
diarylphosphine
oxides.
The
mechanism
studied
via
control
experiments
DFT
calculation.
Moreover,
efficiency
this
highlighted
synthesis
high-value,
structurally
complex
molecules.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 3, 2025
We
report
the
photocatalyzed
three-component
alkene
1,2-alkylpyridylation
reaction
between
alkylboronic
acids,
4-cyanopyridine,
and
an
olefin
to
achieve
pyridination
alkylation
of
synthesis
structurally
diversified
4-alkylpyridines.
The
readily
available
easily
manipulated
acids
were
used
as
alkyl
radical
precursors.
reactions
take
place
under
mild
conditions
with
a
broad
substrate
scope
are
easy
scale
up
gram
level,
they
therefore
potential
practical
value
for
structural
modification
biologically
active
alkylpyridine
derivatives.
The
β-pyridyl
amide
is
a
critical
scaffold
in
medical
discovery
yet
lacks
efficient
synthetic
methods.
Here,
we
describe,
for
the
first
time,
visible-light-induced,
redox-neutral
radical
cross-coupling
reaction
involving
alkenes,
oxamic
acids,
and
cyanopyridines
that
offers
versatile
assembly
of
β-pyridylamides.
This
approach
features
mild
conditions,
high
step
efficiency,
substrate
breadth,
providing
green
strategy
alkene
pyridyl-carbamoylation.
Achieving
this
transformation
relies
on
catalytic
system,
which
adeptly
avoids
competing
nucleophilic
carbamoyl
with
electrophilic
pyridyl
radical,
enabling
three-component
tandem
process
chemoselectivity.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 16, 2025
We
report
a
ferrocene-mediated
electrochemical
intermolecular
oxidative
annulation
between
malonates
and
styrenes
that
avoids
the
use
of
excess
oxidants
such
as
Mn(OAc)3.
The
reaction
proceeds
via
presumably
generation
malonyl
radical
adds
to
styrene.
After
further
anodic
oxidation,
resulting
benzylic
carbocation
is
intercepted
by
one
esters
deliver
desired
γ-lactones.
Abstract
The
utilization
of
photo‐induced
processes
in
C−H
functionalization
via
radical
pathways
has
emerged
as
a
highly
promising
strategy
for
the
preparation
and
modification
complex
organic
compounds.
While
current
methods
generating
carbon‐centred
radicals
from
bonds
primarily
focus
on
hydridic
to
yield
nucleophilic
species,
reactivity
potential
applications
electrophilic
derived
protic
remain
largely
unexplored.
In
this
review,
we
aim
shed
light
seminal
findings
regarding
activation
C(sp
3
)−H
while
also
showcasing
noteworthy
examples
formation
process.
Mechanistically
diverse
modes
are
discussed,
unified
by
proton‐coupled
electron
transfer
(PCET)
concepts.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(14), С. 3138 - 3143
Опубликована: Май 11, 2024
Abstract
Visible‐light‐induced
difunctionalization
of
alkenes
is
a
powerful
strategy
for
constructing
complex
molecules.
Herein,
we
disclose
three‐component
1,2‐alkylpyridylation
under
mild
and
photosensitizers‐free
conditions.
UV‐vis
absorption
spectroscopy
studies
NMR
titration
experiments
indicate
that
the
formation
an
EDA
between
4‐alkyl‐DHPs
4‐cyanopyridines.
Primary,
secondary,
tertiary
C(
sp
3
)‐centered
radicals
were
formed
by
homolytic
cleavage
4‐alkyl‐DHPs.
Gram‐scale
synthesis
late‐stage
functionalization
medicinally
relevant
molecules
showed
synthetic
potential
our
methodology.
