Chemical Science,
Год журнала:
2021,
Номер
12(40), С. 13321 - 13330
Опубликована: Янв. 1, 2021
The
development
of
bioconjugation
chemistry
has
enabled
the
combination
various
synthetic
functionalities
to
proteins,
giving
rise
new
classes
protein
conjugates
with
functions
well
beyond
what
Nature
can
provide.
Despite
progress
in
chemistry,
there
are
no
reagents
developed
date
where
reactivity
be
tuned
a
user-defined
fashion
address
different
amino
acid
residues
proteins.
Here,
we
report
that
2-chloromethyl
acryl
serve
as
simple
yet
versatile
platform
for
selective
modification
at
cysteine
or
disulfide
sites
by
tuning
their
inherent
electronic
properties
through
amide
ester
linkage.
Specifically,
derivatives
(acrylamide
acrylate)
obtained
via
and
easily
implemented
one-pot
reaction
based
on
coupling
between
commercially
available
starting
materials
end-group
(amino
group
hydroxyl
group).
2-Chloromethyl
acrylamide
an
linkage
favor
site
fast
kinetics
near
quantitative
conversations.
In
contrast,
acrylate
bearing
undergo
two
successive
Michael
reactions,
allowing
disulfides
bonds
high
labeling
efficiency
good
conjugate
stability.
Chemical Reviews,
Год журнала:
2021,
Номер
121(12), С. 6915 - 6990
Опубликована: Апрель 9, 2021
At
its
basic
conceptualization,
photoclick
chemistry
embodies
a
collection
of
click
reactions
that
are
performed
via
the
application
light.
The
emergence
this
concept
has
had
diverse
impact
over
broad
range
chemical
and
biological
research
due
to
spatiotemporal
control,
high
selectivity,
excellent
product
yields
afforded
by
combination
light
chemistry.
While
designated
as
"photoclick"
have
many
important
features
in
common,
each
own
particular
advantages
shortcomings.
A
more
extensive
realization
potential
requires
broader
understanding
physical
characteristics
specific
reactions.
This
review
discusses
most
frequently
employed
reported
literature:
photomediated
azide–alkyne
cycloadditions,
other
1,3-dipolarcycloadditions,
Diels–Alder
inverse
electron
demand
additions,
radical
alternating
addition
chain
transfer
nucleophilic
additions.
Applications
these
variety
syntheses,
materials
chemistry,
contexts
surveyed,
with
attention
paid
respective
strengths
limitations
reaction
how
benefits
from
Finally,
challenges
employment
discussed,
along
strategies
opportunities
mitigate
such
obstacles.
Chemical Reviews,
Год журнала:
2021,
Номер
122(2), С. 1752 - 1829
Опубликована: Сен. 21, 2021
Chemically
modified
biomacromolecules─i.e.,
proteins,
nucleic
acids,
glycans,
and
lipids─have
become
crucial
tools
in
chemical
biology.
They
are
extensively
used
not
only
to
elucidate
cellular
processes
but
also
industrial
applications,
particularly
the
context
of
biopharmaceuticals.
In
order
enable
maximum
scope
for
optimization,
it
is
pivotal
have
a
diverse
array
biomacromolecule
modification
methods
at
one's
disposal.
Chemistry
has
driven
many
significant
advances
this
area,
especially
recently,
numerous
novel
visible-light-induced
photochemical
approaches
emerged.
these
reactions,
light
serves
as
an
external
source
energy,
enabling
access
highly
reactive
intermediates
under
exceedingly
mild
conditions
with
exquisite
spatiotemporal
control.
While
UV-induced
transformations
on
biomacromolecules
date
back
decades,
visible
unmistakable
advantage
being
considerably
more
biocompatible,
spectrum
visible-light-driven
now
available,
chiefly
proteins
acids.
This
review
will
discuss
modifications
native
functional
groups
(FGs),
including
functionalization,
labeling,
cross-linking
techniques
well
utility
oxidative
degradation
mediated
by
photochemically
generated
oxygen
species.
Furthermore,
non-native,
bioorthogonal
FGs
be
addressed,
photoclick
chemistry
DNA-encoded
library
synthesis
that
allow
manipulation
activity
biomacromolecule.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(19), С. 10955 - 10982
Опубликована: Янв. 1, 2021
This
review
summarizes
the
most
recent
advances
of
metal-free
late-stage
functionalization
(LSF)
pharmaceutically
relevant
molecules.
Particular
emphasis
is
placed
on
C
–
H
activation
as
well
use
endogenous
functional
groups.
Molecules,
Год журнала:
2022,
Номер
27(3), С. 619 - 619
Опубликована: Янв. 18, 2022
Visible-light
photoredox
catalysis
has
been
established
as
a
popular
and
powerful
tool
for
organic
transformations
owing
to
its
inherent
characterization
of
environmental
friendliness
sustainability
in
the
past
decades.
The
thiol-ene/yne
reactions,
direct
hydrothiolation
alkenes/alkynes
with
thiols,
represents
one
most
efficient
atom-economic
approaches
carbon-sulfur
bonds
construction.
In
traditional
methodologies,
harsh
conditions
such
stoichiometric
reagents
or
specialized
UV
photo-apparatus
were
necessary
suffering
from
various
disadvantages.
particular,
visible-light
also
demonstrated
be
greener
milder
protocol
reactions
recent
years.
Additionally,
unprecedented
advancements
have
achieved
this
area
during
decade.
review,
we
will
summarize
advances
catalyzed
2015
2021.
Synthetic
strategies,
substrate
scope,
proposed
reaction
pathways
are
mainly
discussed.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(19)
Опубликована: Март 18, 2024
Abstract
Unnatural
amino
acids,
and
their
synthesis
by
the
late‐stage
functionalization
(LSF)
of
peptides,
play
a
crucial
role
in
areas
such
as
drug
design
discovery.
Historically,
LSF
biomolecules
has
predominantly
utilized
traditional
synthetic
methodologies
that
exploit
nucleophilic
residues,
cysteine,
lysine
or
tyrosine.
Herein,
we
present
photocatalytic
hydroarylation
process
targeting
electrophilic
residue
dehydroalanine
(Dha).
This
possesses
an
α
,
β
‐unsaturated
moiety
can
be
combined
with
various
arylthianthrenium
salts,
both
batch
flow
reactors.
Notably,
setup
proved
instrumental
for
efficient
scale‐up,
paving
way
unnatural
acids
peptides
substantial
quantities.
Our
approach,
being
inherently
mild,
permits
diversification
even
when
they
contain
sensitive
functional
groups.
The
readily
available
salts
facilitate
seamless
integration
Dha‐containing
wide
range
arenes,
blueprints,
natural
products,
culminating
creation
unconventional
phenylalanine
derivatives.
synergistic
effect
high
group
tolerance
modular
characteristic
aryl
electrophile
enables
peptide
conjugation
ligation
conditions.
ACS Organic & Inorganic Au,
Год журнала:
2022,
Номер
2(5), С. 422 - 426
Опубликована: Июль 15, 2022
Red-light
enables
deeper
material
penetration,
which
is
important
for
biological
applications
and
has
consequences
chemical
synthesis.
Therefore,
the
search
new
photocatalysts
that
absorb
in
this
region
crucial.
Despite
undeniable
utility
of
porphyrins
blue-
green-light-induced
energy-
electron-transfer
processes,
they
are
also
perfectly
suited
red-light
applications.
Herein,
we
describe
free-base
as
photoredox
catalysts
red-light-induced
organic
transformations.
They
can
act
both
photooxidants
photoreductants
accomplish
synthesis
biaryls
once
merged
with
Pd-catalysis.
The
developed
methodology
holds
promise
broader
applications,
heme-based
protoporphyrin
used
a
photocatalyst
reactions
be
realized
aqueous
conditions.
