Beilstein Journal of Organic Chemistry,
Год журнала:
2024,
Номер
20, С. 3274 - 3280
Опубликована: Дек. 17, 2024
The
rising
popularity
of
bioconjugate
therapeutics
has
led
to
growing
interest
in
late-stage
functionalization
(LSF)
peptide
scaffolds.
α,β-Unsaturated
amino
acids
like
dehydroalanine
(Dha)
derivatives
have
emerged
as
particularly
useful
structures,
the
electron-deficient
olefin
moiety
can
engage
reactions,
a
Giese-type
reaction.
Cheap
and
widely
available
building
blocks
organohalides
be
converted
into
alkyl
radicals
by
means
photoinduced
silane-mediated
halogen-atom
transfer
(XAT)
offer
mild
straightforward
methodology
alkylation.
In
this
research,
we
present
metal-free
strategy
for
photochemical
alkylation
derivatives.
Upon
abstraction
hydride
from
tris(trimethylsilyl)silane
(TTMS)
an
excited
benzophenone
derivative,
formed
silane
radical
undergo
XAT
with
bromide
generate
radical.
Consequently,
undergoes
reaction
Dha
forming
new
C(sp
3
)–C(sp
)
bond.
performed
phosphate-buffered
saline
(PBS)
solution
shows
post-functionalization
prospects
through
pathways
involving
classical
chemistry.
Organic Letters,
Год журнала:
2025,
Номер
27(4), С. 1054 - 1059
Опубликована: Янв. 16, 2025
Here,
we
present
a
three-component
successive
radical
addition
strategy
for
the
preparation
of
complex
noncanonical
α-amino
acids
from
easily
available
glycine
derivatives,
alkenes,
and
aryl
sulfonium
salts
via
copper-catalyzed
photoredox-neutral
catalytic
cycle.
The
utility
this
method
is
further
demonstrated
by
its
application
in
late-stage
site-selective
modifications
residues
short
peptides.
It
worth
noting
that
only
1
mol
%
copper
catalyst
required
reaction,
demonstrating
high
efficiency.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июнь 13, 2024
Isotopically
labeled
alkanes
play
a
crucial
role
in
organic
and
pharmaceutical
chemistry.
While
some
deuterated
methylating
agents
are
readily
available,
the
limited
accessibility
of
other
deuteroalkyl
reagents
has
hindered
synthesis
corresponding
products.
In
this
study,
we
introduce
nickel-catalyzed
system
that
facilitates
various
deuterium-labeled
through
hydrodeuteroalkylation
d2-labeled
alkyl
TT
salts
with
unactivated
alkenes.
Diverging
from
traditional
reagents,
thianthrenium
(TT)
can
effectively
selectively
deuterium
at
α
position
chains
using
D
Organic Letters,
Год журнала:
2024,
Номер
26(25), С. 5323 - 5328
Опубликована: Июнь 17, 2024
Amino
acids
and
aromatic
nitrogen
heterocycles
are
widely
used
in
pharmaceuticals.
Herein,
we
present
an
effective
visible-light-driven
thiobenzoic
acid
(TBA)-catalyzed
decyanative
C(sp3)–H
heteroarylation
of
glycine
derivatives.
This
process
occurs
under
mild
straightforward
conditions,
affording
a
range
valuable
yet
challenging-to-obtain
α-heteroaryl
amino
Moreover,
this
organocatalytic
C(sp3)–C(sp2)
bond
formation
reaction
is
applicable
to
the
late-stage
modification
various
short
peptides.
Chemical Communications,
Год журнала:
2024,
Номер
60(75), С. 10378 - 10381
Опубликована: Янв. 1, 2024
Here
we
report
a
visible-light
facilitated
radical
addition
strategy
for
the
preparation
of
various
natural
or
unnatural
α-amino
acids
from
readily
available
glycine
derivatives
and
alkenes.
A
key
aspect
in
achieving
this
side
carbon
chain
introduction
reaction,
while
circumventing
well-documented
cyclization
pathway,
was
employment
radical-polar
crossover
under
redox
neutral
conditions.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
147(9), С. 7533 - 7544
Опубликована: Фев. 21, 2025
α,β-dehydroalanine
(ΔAla)
is
a
uniquely
reactive
nonproteinogenic
amino
acid
often
employed
for
the
late-stage
functionalization
of
peptides,
natural
products
(NPs),
and
proteins.
The
modification
ΔAla
powerful
method
semisynthetic
engineering
NPs
post-translational
protein
mutagenesis.
Numerous
enabling
techniques
have
been
developed
over
years,
but
most
state-of-the-art
approaches
furnish
product
mixtures
detrimental
in
many
applications.
Here,
we
report
Pd(II)-mediated
coupling
reaction
between
aryl
N-methylimidodiacetic
boronates
ΔAla-containing
peptides
proteins
which
yields
ΔzPhe
with
high
selectivity.
proceeds
water
under
ambient
conditions
(37
°C,
<24
h)
without
exclusion
oxygen
using
fully
unprotected
substrates.
speed
selectivity
enabled
by
use
N,N'-ethylene-bis-Lthreonine
as
Pd(II)
ligand.
We
utilize
this
chemistry
to
selectively
functionalize
variety
oligopeptides,
NP-like
compounds,
intact
Finally,
show
that
can
be
readily
adapted
modify
vitro
translated
devising
platform
chemoribosomal
synthesis
ΔzPhe-containing
structures.
Altogether,
our
provides
tool
selective
Asian Journal of Organic Chemistry,
Год журнала:
2024,
Номер
13(11)
Опубликована: Авг. 16, 2024
Abstract
A
new
approach
of
dual
visible
light‐induced
gold(III)‐catalyzed
alkynylation
and
its
application
in
selective
modification
alkyne‐linked
peptides
has
been
developed.
The
bis‐cyclometalated
gold(III)
complex
exhibited
roles
(1)
situ
generation
quinolizinium‐based
photosensitizer
(λ
em
=500
–
594
nm)
(2)
iminium
ions.
Under
optimized
conditions,
alkynylated
products
were
afforded
good
yields
up
to
73
%.
this
strategy
gave
modified
67
%
conversion.
Our
light/gold(III)
catalysis
exemplifies
the
potential
merging
photocatalysis
transition
metal
develop
novel
bioconjugation.
