The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 26, 2024
In
this
work,
a
switchable
synthesis
of
β-ketosulfone
and
α-chloroketone
through
radical
difunctionalization
alkenes
is
reported.
The
transformation
works
well
under
iron
peroxo
species/photoredox
dual
catalysis
an
open-flask
atmosphere,
the
reaction
highlighted
with
good
yields
broad
scope.
Mechanism
studies
show
that
initiated
by
formal
[4
+
2]
cyclization
sulfonyl
in
regioselective
manner.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 31, 2024
Abstract
Introducing
distinctive
functional
groups
to
expand
the
structural
diversity
and
improve
intrinsic
properties
of
parent
molecules
has
been
an
essential
pursuit
in
organic
chemistry.
By
using
perfluoroalkyl
halide
(PFAH)
as
a
nontraditional,
readily
available,
ideal
1,2‐difluoroalkenyl
coupling
partner,
defluorinative
cyclization
reaction
enamides
for
construction
fluoroalkenyl
oxazoles
is
first
developed.
The
selective
controllable
two‐fold
cleavage
vicinal
C(sp
3
)─F
bonds
PFAH
not
only
enables
introduction
specific
moiety
with
ease
but
also
results
functionalization
two
2
)─H
without
need
metal
catalyst,
photocatalyst,
oxidant,
or
light.
method
can
be
applied
late‐stage
modification
complex
molecules,
synthesis
biological‐relevant
oxazole
analoges,
scale‐up
synthesis,
which
all
further
highlight
real‐world
utility
this
protocol.
Mechanistic
studies
reveal
that
possibly
proceeds
through
radical
perfluoroalkylation,
consecutive
C─F
bond
heterolytic
cleavage,
process.
In
addition,
situ
formed
may
serve
hydrogen
abstractor.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(21), P. 4532 - 4536
Published: May 21, 2024
A
binary
Ni/Eu
catalytic
system
has
been
developed,
which
enables
an
efficient
reductive
dicarbofunctionalization
of
unactivated
alkenes
with
alkyl
halides
and
malononitriles.
The
combination
Ni
electron-shuttle
catalysis
Eu(OTf)
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 2, 2025
Unsymmetric
disulfides
are
prevalent
in
natural
products
and
essential
medicinal
chemistry
materials
science,
but
their
robust
synthesis
poses
significant
challenges.
In
this
paper,
we
report
an
expeditous
transition-metal-free
methodology
for
synthesizing
unsymmetric
through
the
addition
of
perthiyl
radicals
to
alkenes.
This
study
marks
use
generating
by
reacting
SO2
with
unactivated
alkyl
(pseudo)halides
(Cl/Br/I/OTs).
Various
primary,
secondary
tertiary
substituted
different
functional
groups
successfully
function
as
suitable
reactants.
The
formation
involvement
reaction
process
verified
mechanistic
studies
DFT
calculations.
Overall,
method
leverages
readily
available
electrophiles
alkenes
alongside
a
single
setup
efficiently
form
both
carbon-sulfur
sulfur-sulfur
bonds
simultaneously.
Here,
authors
novel
transition-metalfree
Organic Chemistry Frontiers,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
A
radical-mediated
sulfonylation
relay
of
alkyl
alkynes/alkenes
with
electron-deficient
alkenes
using
Na
2
S
O
4
as
a
linker
is
developed
to
synthesize
highly
selective
(
Z
)-vinyl
and
sulfones
under
metal-free
catalyzed
system.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 24, 2025
The
δ-lactam
motif
is
a
privileged
pharmacophore
in
drug
design
and
development.
While
these
biologically
relevant
molecules
could
be
assembled
through
two-component
cyclization,
modular
approach
to
constructing
structures
via
multicomponent
reaction
with
unactivated
alkenes
as
starting
materials
rare.
Herein,
we
report
tandem
that
integrates
alkene-dialkylation
radical-involved
ring-opening
cyclization
under
single
metal-electron-shuttle
catalysis,
which
represents
the
most
expeditious
access
fluorinated
δ-lactams
from
simple
alkenes.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 19, 2025
A
novel
Fe-catalyzed
alkylative
aminosulfonylation
of
alkenes
and
alkynes
with
alkyl
halides
O-Ts
activated
hydroxylamines
by
using
Na2S2O4
as
a
reductant
sulfone
source
has
been
developed.
The
metal-electron-shuttle
catalysis
was
discovered
to
be
vital
for
the
highly
efficient
generation
sulfonyl
radicals
anions
without
requiring
organometallic
intermediates.
This
method
provides
access
sulfonamides
from
easily
available
features
broad
substrate
scope.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(22), P. 6340 - 6346
Published: Jan. 1, 2024
We
developed
the
first
transition-metal-catalyzed,
regiodivergent
sulfonylation
of
aziridines,
enabling
efficient
synthesis
diverse
β-amino
sulfones
under
mild
conditions
with
broad
substrate
compatibility
and
high
regioselectivity.
Small,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 16, 2024
Abstract
Intracellular
delivery
of
proteins
has
largely
been
relying
on
cationic
nanoparticles
to
induce
efficient
endosome
escape,
which,
however,
poses
serious
concerns
the
inflammatory
and
cytotoxic
effects.
Herein,
a
versatile
noncationic
nano
biohybrid
platform
is
introduced
for
cytosolic
protein
by
utilizing
nano‐confined
biocatalytic
reaction.
This
constructed
co‐immobilizing
glucose
oxidase
(GOx)
target
into
nanoscale
hydrogen‐bonded
organic
frameworks
(HOFs).
The
reaction
GOx
leveraged
controlled
perturbation
intracellular
redox
homeostasis
sustained
hydrogen
peroxide
(H
2
O
)
production
diminishing
flux
pentose
phosphate
pathway
(PPP).
in
turn
induces
escape
nanobiohybrids.
Concomitantly,
GOx‐mediated
hypoxia
leads
overexpression
azo
reductase
that
initiated
materials'
self‐destruction
releasing
proteins.
These
biological
effects
collectively
highly
delivery.
versatility
this
further
demonstrated
various
types
proteins,
different
loading
approaches
(in
situ
immobilization
or
post‐adsorption),
multiple
cell
lines.
Finally,
efficiency
biosafety
are
tumor‐bearing
mouse
model.
nanohybrid
system
opens
up
new
avenues
expected
be
extensively
applicable
broad
range
biomolecuels.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 24, 2024
Multicomponent
radical
tandem
reactions
have
emerged
as
a
crucial
technique
for
synthesizing
complex
molecules
in
organic
chemistry.
In
this
study,
we
report
palladium-catalyzed
four-component
difluoroalkylative
carbonylation
of
enynes
and
ethyl
difluoroiodoacetate.
This
transformation
proceeds
through
multistep
sequential
reaction
that
introduces
reactive
difluoro
carbonyl
groups
while
constructing
the
benzofuran
skeleton.
Moreover,
variety
valuable
2,3-disubstituted
derivatives
were
obtained
respectable
yields
with
excellent
functional
group
compatibility.
