European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
27(3)
Published: Nov. 30, 2023
Abstract
Since
the
first
report
that
1,2,4,5‐tetrazines
undergo
a
bioorthogonal
reaction
with
dienophiles
in
form
of
an
inverse
electron‐demand
Diels‐Alder
reaction,
demand
for
high‐yielding
synthetic
approaches
towards
them
grew
steadily.
Despite
this
significant
interest,
tetrazines
were
predominantly
accessed
via
Pinner
synthesis
or
other
Pinner‐like
reactions,
significantly
limiting
available
substrates.
In
particular,
unsymmetrically
substituted
s‐tetrazines
selective
conjugation
to
another
species
presented
major
challenge.
To
tackle
these
challenges,
new
and
innovative
transformations
have
been
developed
widen
scope
accessible
symmetric
unsymmetric
tetrazines.
For
instance,
Ni(II),
Zn(II),
sulphur‐catalysed
reactions
between
two
nitriles
hydrazine
developed,
which
provide
access
wide
range
(un‐)symmetric
aryl
s‐tetrazines.
Also,
amidines
orthoesters
give
alkyl
substituents,
whereas
usage
CH
2
Cl
yields
valuable
H‐monosubstituted
Methods
using
thiocarbohydrazides,
terminal
fluoroolefins,
oxetane
esters,
tosyl
hydrazones
are
among
recent
additions.
Due
high
interest
tetrazine
click‐chemistry
approaches,
some
reach
beyond
we
expect
overview
routes
aid
exploration
further
applications
Ultimately,
hope
guide
chemists
chemical
biologists
accessing
functional
Advanced Materials,
Journal Year:
2024,
Volume and Issue:
36(41)
Published: Aug. 16, 2024
Abstract
Bioorthogonal
chemistry
has
provided
an
elaborate
arsenal
to
manipulate
native
biological
processes
in
living
systems.
As
the
great
advancement
of
nanotechnology
recent
years,
bioorthogonal
nanozymes
are
innovated
tackle
challenges
that
emerged
practical
biomedical
applications.
uniquely
positioned
owing
their
advantages
high
customizability
and
tunability,
as
well
good
adaptability
systems,
which
bring
exciting
opportunities
for
More
intriguingly,
offers
opportunity
innovating
catalytic
materials.
In
this
comprehensive
review,
significant
progresses
discussed
with
both
spatiotemporal
controllability
performance
highlight
design
principles
rapid
The
remaining
future
perspectives
then
outlined
along
thriving
field.
It
is
expected
review
will
inspire
promote
novel
nanozymes,
facilitate
clinical
translation.
Journal of Medicinal Chemistry,
Journal Year:
2023,
Volume and Issue:
66(24), P. 16546 - 16567
Published: Dec. 12, 2023
Time-
and
space-resolved
drug
delivery
is
highly
demanded
for
cancer
treatment,
which,
however,
can
barely
be
achieved
with
a
traditional
prodrug
strategy.
In
recent
years,
the
strategy
based
on
bioorthogonal
bond
cleavage
chemistry
has
emerged
advantages
of
high
temporospatial
resolution
over
activation
homogeneous
irrespective
individual
heterogeneity.
past
five
tremendous
progress
been
witnessed
in
this
field
one
such
entering
Phase
II
clinical
trials.
This
Perspective
aims
to
highlight
these
new
advances
(2019–2023)
critically
discuss
their
pros
cons.
addition,
remaining
challenges
potential
strategic
directions
future
will
also
included.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(14)
Published: Jan. 12, 2024
Abstract
The
chemical
modification
of
proteins
serves
as
a
fundamental
tool
for
understanding
biological
processes
and
enables
the
design
biofunctional
materials.
Among
available
methodologies,
photochemical
strategies
have
garnered
significant
attention
because
their
remarkable
biocompatibility
precise
spatiotemporal
reaction
control.
Developing
novel
reactions
tailored
to
specific
applications
necessitates
comprehensive
photoreactive
properties,
including
catalyst
structures,
appropriate
modifiers,
conditions.
This
review
discusses
modifications
using
an
array
catalysts,
photoredox
catalysts
single‐electron
transfer
(SET),
energy
transfer,
long‐wavelength
excitable
photocatalysts,
genetically
encoded
artificial
metalloenzymes.
discussion
covers
unique
attributes,
mechanisms,
practical
applications,
future
prospects
each
catalyst‐driven
reaction,
shedding
light
on
evolving
landscape
protein
modifications.
Current Opinion in Cell Biology,
Journal Year:
2024,
Volume and Issue:
88, P. 102360 - 102360
Published: April 18, 2024
Cells
generate
a
highly
diverse
microtubule
network
to
carry
out
different
activities.
This
is
comprised
of
distinct
tubulin
isotypes,
tubulins
with
post-translational
modifications,
and
many
microtubule-based
structures.
Defects
in
this
complex
system
cause
numerous
human
disorders.
However,
how
subtypes
regulate
cellular
architectures
activities
remains
largely
unexplored.
Emerging
tools
such
as
photosensitive
pharmaceuticals,
chemogenetics,
optogenetics
enable
the
spatiotemporal
manipulation
structures,
dynamics,
cross-linking
actin
filaments
target
subtypes.
review
summarizes
design
rationale
applications
these
new
approaches
aims
provide
roadmap
for
researchers
navigating
intricacies
dynamics
their
modifications
contexts,
thereby
opening
avenues
therapeutic
interventions.
Beilstein Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
21, P. 296 - 326
Published: Feb. 7, 2025
Red-light-activated
photocatalysis
has
become
a
powerful
approach
for
achieving
sustainable
chemical
transformations,
combining
high
efficiency
with
energy-saving,
mild
conditions.
By
harnessing
the
deeper
penetration
and
selectivity
of
red
near-infrared
light,
this
method
minimizes
side
reactions
typical
higher-energy
sources,
making
it
particularly
suited
large-scale
applications.
Recent
advances
highlight
unique
advantages
both
metal-based
metal-free
catalysts
under
red-light
irradiation,
broadening
range
possible
reactions,
from
selective
oxidations
to
complex
polymerizations.
In
biological
contexts,
enables
innovative
applications
in
phototherapy
controlled
drug
release,
exploiting
its
tissue
low
cytotoxicity.
Together,
these
developments
underscore
versatility
impact
photocatalysis,
positioning
as
cornerstone
green
organic
chemistry
significant
potential
synthetic
biomedical
fields.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 19, 2025
Alpha-pyrones
have
been
used
for
applications
ranging
from
total
synthesis
to
antibiotics.
However,
their
application
as
dienes
in
bioorthogonal
reactions
has
not
extensively
explored.
In
previous
work,
we
demonstrated
the
promising
of
ester-functionalized
pyrones
protein
labeling.
Here,
constructed
a
library
substituted
evaluate
potential
by
exploring
relationships
among
structure,
reactivity,
and
bioorthogonality.
We
found
that
most
pyrone
derivatives
with
electron-withdrawing
groups
exhibited
reactivity
toward
endo-bicyclo[6.1.0]nonyne
(BCN),
producing
tricyclic
tetracyclic
products
good
yields.
As
expected,
more
stronger
substituents
showed
faster
reaction
kinetics
BCN.
Bicyclic
substantially
decreased
likely
resulting
increased
steric
effects.
Counterintuitively,
substitutions
at
positions
4
5
affected
than
those
3
6.
To
provide
insights
into
both
expected
counterintuitive
reactivities
members,
performed
quantum
chemical
analysis.
Additionally,
evaluated
each
pyrone's
L-cysteine
no
correlation
between
BCN
cysteine-based
Finally,
collection
popular
dienophiles
reactions.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 30, 2024
The
revolutionary
impact
of
photoredox
catalytic
processes
has
ignited
novel
avenues
for
exploration,
empowering
us
to
delve
into
nature
in
unprecedented
ways
and
pioneer
innovative
biotechnologies
therapy
diagnosis.
However,
integrating
artificial
catalysis
living
systems
presents
significant
challenges,
primarily
due
concerns
over
low
targetability,
compatibility
with
complex
biological
environments,
the
safety
risks
associated
photocatalyst
toxicity.
To
address
these
herein,
we
present
a
bioorthogonally
activatable
approach.
In
this
approach,
potent
selection
via
atom
replacement
rhodamine
core
yielded
(PC-Tz).
introduction
1,2,4,5-tetrazine
quenched
its
photocatalytic
properties,
which
were
restored
upon
an
intracellular
inverse
electron-demand
Diels–Alder
(iEDDA)
reaction
trans-cyclooctene
(TCO)
localized
mitochondria.
This
led
remarkable
oxidation
nicotinamide
adenine
dinucleotide
(NADH),
effectively
manipulating
mitochondrial
electron
transport
chain
(ETC)
under
hypoxic
conditions
cancer
cells.
Additionally,
pyroptotic
cell
death
was
observed
through
caspase-3/gasdermin
E
(GSDME)
pathway,
achieving
notable
antitumor
efficacy
adenosine
triphosphate
(ATP)
reduction
tumor
best
our
knowledge,
represents
first
example
catalysis,
opening
new
chemists
spatiotemporally
control
activity
specific
organelles
without
disrupting
other
native
processes.
