Abstract
This
year
marks
the
10th
anniversary
of
SuFEx
chemistry,
a
field
that
has
witnessed
significant
advancements
over
past
decade.
These
include
efficient
synthetic
strategies
toward
polymerization
via
approach
leading
to
diverse
polymers,
alongside
discovery
new
SuFExable
hubs
and
coupling
conditions.
Non-canonical
reactions,
such
as
deoxyfluorination
on-water
have
also
emerged.
Furthermore,
there
been
substantial
strides
in
radiosynthesis
[18F]
hubs.
review
provides
an
overview
these
developments,
focusing
on
polymerization,
non-canonical
reaction,
radiochemistry
chemistry.
1
Introduction
2
Polymerization
3
Non-Canonical
Reactions
4
Fluorine-18
Radiochemistry
5
Conclusions
Outlook
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(20)
Опубликована: Фев. 28, 2024
Abstract
We
demonstrate
that
electrochemical‐induced
decarboxylation
enables
reliable
post‐polymerization
modification
and
degradation
of
polymers.
Polymers
containing
N
‐(acryloxy)phthalimides
were
subjected
to
electrochemical
under
mild
conditions,
which
led
the
formation
transient
alkyl
radicals.
By
installing
these
redox‐active
units,
we
systematically
modified
pendent
groups
chain
ends
polyacrylates.
This
approach
enabled
production
poly(ethylene‐
co
‐methyl
acrylate)
poly(propylene‐
copolymers,
are
difficult
synthesize
by
direct
polymerization.
Spectroscopic
chromatographic
techniques
reveal
transformations
near‐quantitative
on
several
polymer
systems.
Electrochemical
also
all‐methacrylate
poly(
‐(methacryloxy)phthalimide‐
methacrylate)
copolymers
with
a
efficiency
>95
%.
Chain
cleavage
is
achieved
through
‐hydroxyphthalimide
ester
subsequent
β‐scission
backbone
radical.
Electrochemistry
thus
shown
be
powerful
tool
in
selective
controlled
macromolecular
degradation.
ACS Catalysis,
Год журнала:
2024,
Номер
14(6), С. 4318 - 4328
Опубликована: Март 6, 2024
Sulfonyl
fluorides
have
found
increasing
applications
as
functional
molecules
in
chemistry
and
biology.
We
herein
report
a
copper-catalyzed
atom-economical
access
to
two
categories
of
sulfonyl
through
radical
relay
strategy
the
presence
an
SO2
surrogate.
The
aliphatic
C(sp3)–H
bond
N-fluoro-N-alkyl
sulfonamides
reacted
via
1,5-hydrogen
atom
transfer
(HAT)
process,
affording
alkanesulfonyl
with
proximal
amino
group.
On
other
hand,
utilizing
substrates
containing
proper
C═C
double
resulted
intramolecular
olefin
aminofluorosulfonylation,
allowing
synthesis
fluorosulfonyl-functionalized
pyrrolidines
piperidines
atom-transfer
addition
(ATRA).
Both
reaction
systems
proceeded
under
mild
conditions,
requiring
no
additional
fluorine
source.
Experimental
computational
studies
suggest
that
S–F
coupling
is
likely
achieved
radical-rebound
pathway.
By
taking
advantage
SuFEx
multifunctionality
products,
method
applicable
late-stage
modification
bioactive
compounds,
drug
ligation
chemistry,
organic
synthesis.
Chemical Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 2, 2024
Click
chemistry
has
become
one
of
the
most
powerful
construction
tools
in
field
organic
chemistry,
materials
science,
and
polymer
as
it
offers
hassle-free
platforms
for
high-yielding
synthesis
novel
easy
functionalization
strategies.
The
absence
harsh
reaction
conditions
or
complicated
workup
procedures
allowed
rapid
development
biofunctional
polymeric
materials,
such
biopolymers,
tailor-made
surfaces,
stimulus-responsive
polymers,
etc.
In
this
review,
we
discuss
various
types
click
reactions─including
azide-alkyne
cycloadditions,
nucleophilic
radical
thiol
reactions,
a
range
cycloadditions
(Diels-Alder,
tetrazole,
nitrile
oxide,
etc.),
sulfur
fluoride
exchange
(SuFEx)
reaction,
oxime-hydrazone
reactions─and
their
use
formation
study
polymers.
Following
that,
state-of-the-art
biological
applications
"click"-biofunctionalized
including
both
passive
(e.g.,
biosensing
bioimaging)
"active"
ones
that
aim
to
direct
changes
biosystems,
e.g.,
drug
delivery,
antiviral
action,
tissue
engineering.
conclusion,
have
outlined
future
directions
existing
challenges
click-based
polymers
medicinal
clinical
applications.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
11(1), С. 217 - 235
Опубликована: Ноя. 14, 2023
This
review
summarizes
the
latest
achievements
in
photochemical
and
electrochemical
strategies
for
synthesis
of
sulfonyl
fluorides
focuses
on
novel
features
proposed
mechanisms.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(19), С. 13536 - 13545
Опубликована: Май 2, 2024
Herein,
we
establish
a
remote
hydrosulfonamidation
(HSA)
of
alkenes
using
palladium
catalysis,
where
N-fluoro-N-(fluoro-sulfonyl)-carbamate
with
sulfur(VI)
fluoride
moiety
is
demonstrated
as
good
amidation
reagent.
The
anti-Markovnikov
HSA
reaction
terminal
and
the
internal
are
achieved
to
efficiently
yield
primary
N-alkyl-N-(fluorosulfonyl)-carbamates.
In
addition,
this
protocol
enables
high-value
utilization
alkane
by
combining
dehydrogenation
process.
generated
N-alkyl
products
exhibit
unique
reactivity
fluorides,
which
can
be
directly
transferred
sulfamides
or
amines
via
exchange
reaction,
thereby
streamlining
their
synthesis.
Moreover,
(pyridyl)
benzazole-type
ligand
proved
vital
for
excellent
chemo-
regioselectivities.
RSC Applied Polymers,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
We
present
a
new
coarse-grained
model
and
molecular
simulation
study
of
polysulfamide,
class
polymer
that
could
be
sustainable
alternative
to
commodity
polymers
like
polyurea.
Macromolecules,
Год журнала:
2023,
Номер
56(13), С. 5033 - 5049
Опубликована: Июнь 28, 2023
In
this
paper,
we
present
a
synergistic,
experimental,
and
computational
study
of
the
self-assembly
N,N′-disubstituted
polysulfamides
driven
by
hydrogen
bonds
(H-bonds)
between
H-bonding
donor
acceptor
groups
in
repeating
sulfamides
as
function
structural
design
polysulfamide
backbone.
We
developed
coarse-grained
(CG)
model
that
captures
directionality
H-bonds
sulfamide
used
molecular
dynamics
(MD)
simulations
to
these
polymers
implicit
solvent.
The
CGMD
approach
was
validated
reproducing
experimentally
observed
trends
extent
crystallinity
for
three
synthesized
with
aliphatic
and/or
aromatic
units.
After
validation
our
approach,
computationally
predicted
effect
repeat
unit
bulkiness,
length,
uniformity
segment
lengths
on
orientational
positional
order
among
self-assembled
chains,
providing
key
principles
tuning
experiments.
Those
predictions
were
then
tested
through
synthesis
characterization
architectures.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(22), С. 15658 - 15665
Опубликована: Окт. 30, 2023
Here
we
report
the
first
asymmetric
synthesis
of
large
chiral
macrocycles
with
sulfur
atoms.
Building
on
stereospecific
SuFEx
and
SuPhenEx
click
chemistries,
this
approach
utilizes
disulfonimidoyl
fluorides
p-nitrophenolates─which
are
efficient
building
blocks
two
centers,
diphenols
to
efficiently
form
novel
S–O
bonds.
Characteristic
results
include
enantiospecific
one-step
rings
consisting
21–58
members
characterization
both
enantiomers
(R,R
S,S)
by
e.g.
X-ray
crystallography.
Chemistry of Materials,
Год журнала:
2023,
Номер
35(23), С. 10030 - 10040
Опубликована: Ноя. 29, 2023
Anionic
polymerized
ionic
liquids
with
a
fixed
sulfonylimide
group
have
emerged
as
promising
materials
for
energy
storage
applications,
electromechanical
devices,
and
gas
separation
membranes
due
to
their
highly
delocalized
anionic
charges.
However,
synthetic
challenges
limited
the
production
of
high-purity
poly(sulfonylimide)s
at
scale
hindered
systematic
evaluation
properties.
We
report
route
monomers
>10
g
scales
using
sulfur(VI)
fluoride
exchange
(SuFEx)
click
reaction.
Pendent
acrylate
1-ethyl-3-methylimidazolium
counterions
were
synthesized
perfluorinated
side
groups
different
lengths
cross-linked
form
ionoelastomers.
The
networks
stretchable
(≈120%
strain
break),
showed
high
solvent-free
conductivity
(>3.8
×
10–3
mS/cm),
hydrophobic
water
contact
angles
>105°.
imidazolium
interact
strongly
chains,
yielding
nonmonotonic
trends
in
modulus
relative
glass
transition
temperature
(Tg).
Wide-angle
X-ray
scattering
vibrational
spectroscopies
reveal
that
shorter
promote
cation
dissociation,
while
longer
chains
cause
aggregation.
expect
this
SuFEx
approach
will
expand
access
next-generation
poly(sulfonylimide)
electrolytes
variety
applications
here
demonstrate
its
utility
providing
new
insight
into
molecular-level
design
