Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 4, 2024
Difluoromethylene
and
pyridine
cores
are
very
important
structural
units
in
medicinal
chemistry.
Herein,
we
report
the
development
of
photoredox-catalyzed
ring-opening
1,3-alkoxypyridylation
gem-difluorinated
cyclopropanes
using
4-cyanopyrines
alcohols,
employing
cyclopropane
radical
cations
as
key
intermediate.
The
reaction
exhibits
high
regioselectivity
under
mild
conditions
can
also
be
practiced
on
gram-scale
synthesis,
telescoped
reaction,
late-stage
functionalization
biological
molecules.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(12), P. 4564 - 4570
Published: Jan. 1, 2024
We
present
NHC-catalyzed
atroposelective
esterification
of
prochiral
dialdehydes,
delivering
enantioenriched
axially
chiral
diaryl
ethers.
Matched
kinetic
resolutions
amplify
the
enantioselectivity
by
removing
minor
enantiomers
via
over-functionalization.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 13, 2024
ConspectusIn
recent
years,
radical-mediated
cross-coupling
reactions
have
emerged
as
a
compelling
strategy
for
achieving
rich
diversity
in
molecular
topologies
under
benign
conditions.
However,
the
inherent
high
reactivity
of
radicals
presents
considerable
challenges
controlling
reaction
pathways
and
selectivity,
which
often
results
limited
range
substrates
constrained
profile.
Given
capacity
visible-light
photoredox
catalysis
to
generate
wide
variety
reactive
radical
ions
controlled
manner
propensity
copper
complexes
toward
species,
we
envisaged
that
synergy
between
chiral
catalysts
photoactive
would
pave
way
developing
innovative
strategies.
This
integration
is
poised
unlock
broad
spectrum
enantioselective
multicomponent
reactions.In
this
Account,
describe
our
insights
efforts
realm
reactions.
These
advancements
been
achieved
through
application
dual
photoredox/copper
or
bifunctional
visible
light
irradiation.
Our
work
systematically
divided
into
two
sections
based
on
activation
modes.
The
first
section
focuses
photoinduced
copper-catalyzed
C-C
C-O
bond
formation
addition/nucleophilic
trap
sequence.
discussion
particularly
concentrated
asymmetric
carbocyanation
carboarylation
vinylarenes,
1,3-enynes,
1,3-dienes.
findings
underscore
irradiation
with
can
adeptly
modulate
pace
generation,
thus
orchestrating
consecutive
stages
ensuring
attainment
both
chemo-
stereoselectivity.
In
domain
formation,
leveraging
carboxylic
acids
nucleophilic
oxygen
source,
introduce
suite
esterification
benzylic,
allylic,
propargylic
radicals.
are
derived
from
precursors,
showcasing
versatility
approach.
following
highlights
discovery
field
catalysis,
enables
three-component
transformations
via
direct
aromatic
alkenes.
methodology
begins
generation
formal
distonic
anions
photocatalytic
single-electron
reduction
alkenes,
thus,
enabling
orthogonal
reactivity.
Employing
H
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(48)
Published: Oct. 11, 2023
Abstract
N
‐Heterocyclic
carbene
(NHC)
catalyzed
radical‐radical
reactions
have
been
proven
to
be
powerful
strategies
for
assembling
ketyl‐containing
compounds
via
single
electron
transfer
(SET)
pathway
under
either
thermal
conditions
or
photoredox
conditions.
In
this
context,
acylation
of
alkenes
radical
relay
NHC‐organocatalysis
has
also
opened
a
new
window
the
difunctionalization
construct
valuable
molecules
in
organic
synthesis.
review,
advances
and
progress
were
summarized
according
different
ways
generation
key
NHC‐bound
ketyl‐type
radicals.
Furthermore,
reaction
scopes,
limitations
mechanisms
discussed
based
on
types
catalytic
systems.
Conclusions
perspectives
put
forward
at
end.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(62)
Published: Aug. 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.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
15(4), P. 1418 - 1423
Published: Dec. 14, 2023
Difunctionalization
of
alkenes
is
an
efficient
strategy
for
the
synthesis
complex
compounds
from
readily
available
starting
materials.
Herein,
we
developed
a
copper-catalyzed
visible-light-mediated
trichloromethylative
carbonylation
ethylene
by
employing
commercially
CCl
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(11), P. 3089 - 3099
Published: Jan. 1, 2024
NHC
and
photocatalysis
dual-catalyzed
mono/difluoromethylative
acylation
of
1,3-enynes
was
realized,
providing
fluormethyl-substituted
allenyl
ketones.
SO
2
might
play
a
critical
role
in
achieving
high
reactivity
selectivity.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(29), P. 6114 - 6119
Published: July 5, 2024
Difunctionalization
of
alkynes
has
gained
a
lot
interest
in
current
organic
chemistry.
Herein,
we
developed
an
electrophotocatalytic
multicomponent
cascade
reaction
and
indoles
with
sulfinic
acid
sodium
salts
using
elemental
tellurium
as
the
source.
Using
synergistic
anodic
oxidation
visible-light
irradiation,
various
β-(telluro)vinyl
sulfones
have
been
prepared.
This
strategy
features
mild
conditions,
excellent
substrate
scope,
readily
available
starting
materials,
great
functional
group
tolerance.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(47), P. 32235 - 32242
Published: Nov. 13, 2024
The
direct
use
of
readily
available
aldehydes
as
acyl
radical
precursors
has
facilitated
diverse
three-component
acylative
difunctionalization
reactions
alkenes,
offering
a
powerful
route
to
synthesize
β-branched
ketones.
However,
asymmetric
alkenes
with
still
remains
elusive.
Here
we
report
copper-catalyzed
acylarylation
vinylarenes
and
aryl
boronic
acids.
This
method
begins
formation
from
an
aldehyde
via
hydrogen
atom
transfer.
adds
the
alkene,
forming
new
benzylic
that
then
undergoes
enantioselective
arylation.
A
chiral
binaphthyl-tethered
bisoxazoline
ligand
is
essential
for
achieving
high
stereocontrol.
strategy
enables
synthesis
range
synthetically
valuable
β,β-diaryl
ketones
vinylarenes.
