Monomer Design Enables Mechanistic Mapping of Anionic Ring‐Opening Polymerization of Aromatic Thionolactones
Angewandte Chemie International Edition,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 22, 2025
Degradable
chalcogenide
polyesters,
e.g.,
polythioesters
(PTEs),
typically
exhibit
improved
thermal,
mechanical,
and
optical
properties.
Anionic
ring-opening
polymerization
(ROP)
of
thionolactones,
an
intrinsically
promising
yet
underexplored
approach
to
accessing
PTEs,
however,
is
still
limited
by:
intolerance
metal
catalysts,
inadequate
control
over
chain
growth,
the
absence
aromatic
system.
Monomer
design-boosted
mechanistic
studies
may
address
above
challenges.
Here,
we
present
a
new
highly
reactive
thionolactone
synthesized
from
1,1'-binaphthyl-2,2'-diol
(BINOL).
Our
investigations
into
kinetics
thermodynamics
have
underscored
importance
rapid
initiation,
eventually
leading
discovery
tetrabutylammonium
2-naphthyl-thiocarboxylate
as
distinctive
initiator
that
enables
genuinely
controlled
living
thionolactones.
Ultimately,
atropisomerism
inherent
in
BINOL
has
resulted
creation
axially
chiral
PTE
materials
with
tailored
molecular
weights,
enantiomeric
compositions,
topologies.
Язык: Английский
Monomer Design Enables Mechanistic Mapping of Anionic Ring‐Opening Polymerization of Aromatic Thionolactones
Angewandte Chemie,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 22, 2025
Abstract
Degradable
chalcogenide
polyesters,
e.g.,
polythioesters
(PTEs),
typically
exhibit
improved
thermal,
mechanical,
and
optical
properties.
Anionic
ring‐opening
polymerization
(ROP)
of
thionolactones,
an
intrinsically
promising
yet
underexplored
approach
to
accessing
PTEs,
however,
is
still
limited
by:
intolerance
metal
catalysts,
inadequate
control
over
chain
growth,
the
absence
aromatic
system.
Monomer
design‐boosted
mechanistic
studies
may
address
above
challenges.
Here,
we
present
a
new
highly
reactive
thionolactone
synthesized
from
1,1′‐binaphthyl‐2,2′‐diol
(BINOL).
Our
investigations
into
kinetics
thermodynamics
have
underscored
importance
rapid
initiation,
eventually
leading
discovery
tetrabutylammonium
2‐naphthyl‐thiocarboxylate
as
distinctive
initiator
that
enables
genuinely
controlled
living
thionolactones.
Ultimately,
atropisomerism
inherent
in
BINOL
has
resulted
creation
axially
chiral
PTE
materials
with
tailored
molecular
weights,
enantiomeric
compositions,
topologies.
Язык: Английский
Degradable Polydithioacetals with Adjustable Mechanical Properties and Insights into Entropy-Driven Ring-Opening Polymerization
Macromolecules,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 17, 2025
Язык: Английский
Diastereoselective Formal [3+3] Cascade Cyclization towards Fused 4‐Fluoroalkylated 3,4‐Dihydro‐2H‐pyrans via Copper Catalysis
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 25, 2025
Comprehensive
Summary
The
cycloaddition
and
annulation
reactions
offer
a
powerful
method
toward
various
important
substituted
3,4‐dihydro‐2
H
‐pyran
architectures.
Nevertheless,
the
transformation
for
preparing
fused‐polycyclic
ones
still
remains
challenging
yet
highly
desirable
until
now.
Herein,
we
report
novel
formal
[3+3]
cascade
cyclization
reaction
to
provide
lactam‐fused
4‐fluoroalkylated
3,4‐dihydropyran
skeletons
bearing
three
contiguous
tertiary
carbon
centers
via
copper
catalysis.
Of
note,
these
annulations
proceeded
in
an
exclusively
diastereoselective
manner
through
successive
inert
C(sp
2
)‐Cl
3
)‐H
functionalization,
which
exhibited
site‐selectivity
stereoselectivity.
Additionally,
evaluations
on
biological
activities
of
obtained
products
revealed
that
several
display
inhibitory
activity
against
Siha
H1975
cancer
cell
lines.
Язык: Английский
Adrinogenic Colon Cancer Treatment Using Poly (β-Amino Esters) (PBAEs): Mechanistic Insights, Advanced Utilization Approaches, and Future Directions
Journal of Macromolecular Science Part B,
Год журнала:
2025,
Номер
unknown, С. 1 - 17
Опубликована: Апрель 27, 2025
Язык: Английский
Dye-Sensitized Lanthanide-Doped Upconversion Nanoprobes for Homocysteine Sensing in Human Serum and Living Cells via a Spatial Optimization Strategy
Journal of Materials Chemistry B,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
dye-sensitized
upconversion
nanoprobe
was
developed
for
the
specific
detection
of
Hcy.
It
exhibits
excellent
sensitivity
and
rapid
response
has
been
applied
to
quantitative
Hcy
in
serum
as
well
cell-specific
imaging.
Язык: Английский
Aza-Michael Addition–Fragmentation Ring-Opening Polymerization
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 20, 2025
Cleaving
the
C(sp3)-N
bonds
in
unstrained
cyclic
monomers
for
ring-opening
polymerization
remains
a
formidable
challenge
polymer
chemistry.
Here,
we
report
novel
strategy
that
integrates
cascade
aza-Michael/retro-aza
Michael
reaction
with
chain
growth
mechanism.
For
first
time,
this
approach
cleaves
bond
less-strained
under
ambient
conditions,
yielding
cinnamate-containing
polyamines
controlled
molecular
weight,
narrow
dispersity,
and
unexpected
cis-stereoselectivity.
A
linear
relationship
between
number-average
weight
conversion,
high
chain-end
fidelity,
efficient
extension
proved
excellent
control
over
process.
In
addition,
density
functional
theory
calculations
were
conducted
to
clarify
origin
of
observed
stereoselectivity.
The
versatility
was
further
demonstrated
through
copolymerization
aziridine
synthesis
sequence-controlled
polymers.
This
protocol
provides
new
C-N
cleavage
pattern
would
lead
more
useful
synthetic
pathway
polymers
main-chain
functionalities.
Язык: Английский