Diaryliodonium
salts
are
bench
stable
aryl
radical
precursors.
While
photocatalysts
generally
responsible
for
generation,
recent
reports
have
emerged
exhibiting
photocatalyst-free
generation
using
select
Lewis
bases
as
activators.
Herein,
we
demonstrate
1)
the
ability
of
numerous
to
enable
light-driven
and
2)
these
radicals
can
be
captured
by
transition-metals
coupling
reactions.
These
results
first
step
toward
developing
new
organometallic
reactions
without
photocatalysts.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(12), P. 1399 - 1406
Published: Feb. 29, 2024
Comprehensive
Summary
A
general
and
convenient
photoredox‐catalyzed
acylation
alkylcyanation
of
MBH
acetates
has
been
established,
enabling
the
assembly
C(sp
2
)–C(sp
3
)
bond
by
a
nitrogen‐centered
radical
strategy
for
synthesis
trisubstituted
alkenes
in
moderate
to
excellent
chemical
yields
(48
examples
total).
The
reaction
with
acyl
(indanone)
oxime
esters
afforded
containing
1,4‐dicarbonyl
groups.
Interestingly,
use
Eosin
Y
as
photocatalyst
catalytic
system
resulted
formation
distal
cyano
group‐anchored
via
deconstructive
functionalization
cycloketone
esters.
Notably,
these
resulting
compounds
could
be
applied
late‐stage
transformations,
providing
important
methods
dihydropyridazin‐3(2
H
)‐one.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(15), P. 3189 - 3194
Published: April 8, 2024
A
new
umpolung
approach
to
the
C3–H
functionalization
of
indoles
with
diverse
nucleophiles
based
on
intermediate
formation
I(III)
reagents
is
described.
The
3,5-dimethylisoxazol-4-yl
auxiliary
allows
for
selective
indole
transfer
under
catalyst-free
conditions,
which
was
impossible
using
previously
reported
reagents.
Combining
mildness
transition-metal-free
conditions
and
high
reactivity
hypervalent
iodine
reagents,
this
protocol
tolerates
various
functional
groups
provides
access
that
are
difficult
prepare
conventionally.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(7), P. 4877 - 4887
Published: March 8, 2024
General
and
convenient
visible-light-promoted
alkylsulfonylation
cyanoalkylsulfonylation
of
MBH
adducts
have
been
developed
through
the
multicomponent
insertion
sulfur
dioxide,
enabling
assembly
two
C–S
bonds
to
generate
structurally
diverse
allylic
alkylsulfones
(43
examples
in
total).
The
reaction
with
potassium
alkyltrifluoroborates
1,4-diazabicyclo[2.2.2]octane
bis(sulfur
dioxide)
adduct
afforded
sulfones
generally
good
yields.
Notably,
addition
N,N,N′,N′-tetramethylethylenediamine
as
a
base
into
photocatalytic
system
led
yielding
an
alkyl
sulfonyl
unit
cyano
group-anchored
trisubstituted
alkenes
by
utilizing
cycloketone
oxime
esters
C-radical
precursors.
Both
these
reactions
constructed
bonds,
all
desired
products
were
obtained
moderate
excellent
yields
complete
stereospecificity.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 9, 2025
Sulfone
motifs
play
important
roles
in
bioactive
compounds
and
functional
materials.
The
development
of
efficient
methodologies
for
constructing
sulfonyl-containing
has
thus
attracted
considerable
attention.
Here,
we
introduce
a
protocol
the
preparation
alkyl
aryl
sulfones
under
mild
conditions.
This
employs
β-thioamide
sulfone
as
novel
motif
donor.
It
forms
sulfinates
situ
basic
conditions,
which
then
undergo
cross-coupling
with
intermediates
that
were
generated
from
ligand-free
copper-catalyzed
cyclopropenes
(CPEs)
ring
opening.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 10, 2025
A
palladium-catalyzed
decarboxylative
allylic
sulfonylation
reaction
of
vinyloxazolidine-2,4-diones
with
inexpensive
and
readily
available
sodium
sulfinates
as
reagents
has
been
developed.
Under
the
catalysis
Pd(PPh3)4,
a
wide
range
γ-sulfonyl-α,β-unsaturated
amides
can
be
synthesized
in
good
to
excellent
yields.
The
developed
protocol
is
characterized
by
exclusive
regioselectivity,
mild
conditions,
broad
substrate
scope,
functional
group
tolerance,
suitable
for
gram-scale
synthesis.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
A
transition-metal-free
protocol
for
the
unsymmetrical
radical
1,3-difunctionalization
of
alkenes
has
been
established
first
time
in
form
1,3-difluoroalkylcarboxylation
by
a
photocatalytic
three-component
reaction
allyl
formates,
trifluoroacetanilides,
and
cesium
formate.
This
employs
formate
as
carboxylating
reagent
trifluoroacetanilide
difluoroalkylating
via
C-F
bond
activation.
As
result,
series
previously
inaccessible
difluorinated
adipic
acid
derivatives
can
be
easily
efficient
prepared.
Mechanism
studies
reveal
that
triple
kinetic-controlled
self-ordering
is
key
to
this
unique
reaction.
sorting
involves
fast
initiation
CO2
anion
its
chemoselective
addition
reduction,
followed
slow
generation
fluoroalkyl
chemo-/regioselective
addition.
Notably,
strategy
also
suitable
cyclic
through
diastereoselectively
constructing
two
or
three
consecutive
stereocenters.
Chemical Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 7, 2025
Constructing
chemical
bonds
under
green
sustainable
conditions
has
drawn
attention
from
environmental
and
economic
perspectives.
The
dissociation
of
(hetero)aryl-halide
is
a
crucial
step
most
arylations
affording
(hetero)arene
derivatives.
Herein,
we
summarize
the
(hetero)aryl
halides
activation
enabling
direct
(hetero)arylation
trapping
reagents
construction
highly
functionalized
(hetero)arenes
benign
conditions.
strategies
for
aryl
iodides
are
classified
into
(a)
hypervalent
iodoarene
followed
by
functionalization
thermal/photochemical
conditions,
(b)
aryl-I
bond
in
presence
bases
with/without
organic
catalysts
promoters,
(c)
photoinduced
presence/absence
organophotocatalysts,
(d)
electrochemical
direct/indirect
electrolysis
mediated
organocatalysts
mediators
acting
as
electron
shuttles,
(e)
electrophotochemical
redox-active
organocatalysts.
These
modes
result
exhibiting
diverse
reactivity
formal
cations/radicals/anions
aryne
precursors.
coupling
these
reactive
intermediates
with
leads
to
facile
selective
formation
C-C
C-heteroatom
bonds.
ecofriendly,
inexpensive,
functional
group-tolerant
offer
alternatives
transition
metal-based
catalysis.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 16, 2025
A
photocatalytic
radical
sulfonarylation
of
N-arylacrylamides
via
a
three-component
cascade
cyclopropyl
alcohol
ring
opening/sulfur
dioxide
insertion/sulfonyl
addition/cyclization
sequence
has
been
developed.
This
method
employs
alcohols
as
the
precursors
β-carbonyl
alkyl
radicals
and
Na2S2O5
cheap
source
sulfur
dioxide.
By
using
this
procedure,
wide
variety
γ-keto-sulfone-substituted
oxindoles
were
facilely
synthesized.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(9), P. 2063 - 2071
Published: Feb. 29, 2024
Abstract
Herein,
we
demonstrate
that
carbamoyl
radicals
generated
through
an
organophotocatalytic
protocol
from
4‐carbamoyl‐dihydropyridines
(carbamoyl‐DHPs)
can
be
incorporated
into
Morita‐Baylis‐Hillman
(MBH)
carbonates,
affording
a
range
of
polyfunctionalized
scaffolds
with
yields
ranging
63–98%.
Reaction
monitoring
experiments,
scale‐up,
reuse
the
organophotocatalyst,
and
hydrogenation
succinamic
ester's
alkene
moiety
was
also
conducted,
in
order
to
showcase
mechanistic
features
robustness
this
photochemical
protocol.
