The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(18), P. 13518 - 13529
Published: Sept. 10, 2024
A
three-component
defluorinative
haloalkylation
of
alkenes
with
trifluoromethyl
compounds
and
TBAX
(X
=
Cl,
Br)
via
dual
photoredox/copper
catalysis
is
reported.
The
mild
conditions
are
compatible
a
wide
array
activated
aromatics
bearing
diverse
substituents,
various
nonactivated
terminal
internal
alkenes,
enabling
straightforward
access
to
synthetically
valuable
γ-gem-difluoroalkyl
halides
high
efficiency.
Mechanistic
studies
indicate
that
the
[Cu]
complexes
not
only
serve
as
XAT
catalysts
but
also
facilitate
SET
reduction
groups
by
photocatalysts.
Additionally,
resulting
alkyl
halide
products
can
versatile
conversion
intermediates
for
synthesis
range
compounds.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 7, 2025
We
describe
an
efficient
acyl
esterification
method
for
alkenes
utilizing
acyloxime
esters
as
bifunctional
reagents
featuring
radical
acylation
and
congested
C–O
bond
formation.
This
approach
is
characterized
by
mild
photoredox
conditions,
high
step
atom
economy,
a
broad
substrate
scope,
excellent
regioselectivity.
A
variety
of
valuable
α-acyl
hindered
alcohol
esters,
including
those
obtained
via
gram-scale
synthesis
late-stage
functionalization
pharmaceutical
molecules,
were
presented,
demonstrating
its
synthetic
potential
practicability.
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
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(32)
Published: May 24, 2024
Abstract
Radical‐involved
multicomponent
difunctionalization
of
1,3‐dienes
has
recently
emerged
as
a
promising
strategy
for
rapid
synthesis
valuable
allylic
compounds
in
one‐pot
operation.
However,
the
expansion
radical
scope
and
enantiocontrol
remain
two
major
challenges.
Herein,
we
describe
an
unprecedented
photoinduced
copper‐catalyzed
highly
enantioselective
three‐component
1,2‐azidooxygenation
with
readily
available
azidobenziodazolone
reagent
carboxylic
acids.
This
mild
protocol
exhibits
broad
substrate
scope,
high
functional
group
tolerance,
exceptional
control
over
chemo‐,
regio‐
enantioselectivity,
providing
practical
access
to
diverse
azidated
chiral
esters.
Mechanistic
studies
imply
that
copper
complex
is
implicated
bifunctional
catalyst
both
photoredox
catalyzed
azidyl
generation
C−O
cross‐coupling.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(50), P. 6340 - 6361
Published: Jan. 1, 2024
In
this
review,
the
state-of-the-art
advances
in
radical-involved
C(sp
3
)–N
bond
formation
via
metallaphotoredox
catalysis
have
been
highlighted,
which
are
organized
according
to
different
catalytic
modes,
reaction
types,
and
substrate
classes.
EES Catalysis,
Journal Year:
2024,
Volume and Issue:
2(4), P. 884 - 910
Published: Jan. 1, 2024
Achieving
value-added
transformation
of
chemicals
through
green
catalytic
technology
can
simultaneously
meet
the
market
and
environmental
protection.
This
article
reviews
recent
advances
in
synthesizing
using
piezo-(photo)catalytic
technologies.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(5)
Published: Dec. 9, 2023
Abstract
A
regioselectivity
reversed
three‐component
defluorinative
alkylboration
of
alkenes
with
trifluoromethyls
and
bis(pinacolato)diboron
via
dual
photoredox/copper
catalysis
is
reported.
The
mild
conditions
are
compatible
a
wide
array
nonactivated
trifluoromethyl
aromatics
bearing
electron‐donating
or
electron‐neutral
substituents,
trifluoroacetamides,
various
terminal
internal
alkenes,
enabling
straightforward
access
to
synthetically
valuable
γ
‐
gem
‐difluoroalkyl
boronates
high
efficiency.
Furthermore,
this
protocol
applicable
alkene‐tethered
furnish
‐difluoromethylene‐containing
cyclic
compounds.
Synthetic
applications
preliminary
mechanistic
studies
also
presented.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(18), P. 5232 - 5277
Published: Jan. 1, 2024
This
review
describes
recent
advances
in
the
generation
of
aryl
radicals
using
light
and
electricity.
Such
modern
techniques
allow
for
efficient
energy
resource
utilization,
thus
providing
more
sustainable
radical
arylation
methods.
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
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(38), P. 7009 - 7013
Published: Sept. 14, 2023
The
1,2-iminylalkylation
of
diazenes
using
alkyl
iodides
in
combination
with
an
O-benzoyl
oxime
is
reported.
In
this
transformation,
acted
as
a
radical
precursor
and
XAT
mediator.
addition
to
common
iodides,
other
such
iodomethane,
iodomethane-d3,
trifluoroiodomethane,
ethyl
difluoroiodoacetate,
iodoalkanes
containing
unprotected
hydroxyl
amide
groups
can
also
serve
C-radical
precursors
the
electrophilic
acceptors.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(20), P. 5190 - 5197
Published: Jan. 1, 2023
An
efficient
and
rapid
iron-catalyzed
oxosulfonylation
of
alkynes
with
small-ring
compounds
Na
2
S
O
5
for
the
synthesis
β
-keto
sulfones
has
been
developed.
