Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(41), P. 8674 - 8679
Published: Oct. 7, 2024
The
traditional
intermolecular
O-H
insertion
strategy
is
typically
associated
with
the
reactivity
exhibited
by
singlet
spin
state,
or
it
can
alter
state
from
triplet
to
hydrogen
bonding.
Herein,
we
report
diazoarylidene
succinimide
that
generates
a
persistent
ground-state
carbene
under
visible
light
(Blue
LED,
456
nm)
without
photosensitizer.
This
undergoes
an
intramolecular
via
atom
transfer,
forming
aryloxy
radical
altering
its
and
leading
biologically
relevant
2
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.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 7, 2025
Photocatalytic
proximity
labeling
has
emerged
as
a
valuable
technique
for
studying
interactions
between
biomolecules
in
cellular
context,
providing
precise
spatiotemporal
control
over
protein
labeling.
One
significant
advantage
of
these
methods
is
their
modularity,
allowing
the
use
single
photocatalyst
with
different
reactive
probes
to
expand
interactome
coverage
and
capture
diverse
interactions.
Despite
advances,
fewer
have
been
developed
using
red-light
excitation,
limiting
photoproximity
more
complex
media
such
tissues
animal
models.
Herein,
we
develop
platform
under
utilizing
catalyst
two
distinct
probe
types.
We
first
design
carbene
based
system
that
utilizes
sulfonium
diazo
probes.
This
successfully
applied
on
A549
cells
epidermal
growth
factor
receptor
(EGFR)
Cetuximab-Chlorin
e6
conjugate.
Benchmarking
against
established
techniques
indicates
this
approach
performs
comparably
leading
carbene-based
methods.
Next,
leverage
strong
singlet
oxygen
generation
(SOG)
ability
Chlorin
establish
an
alternative
aniline
hydrazide
EGFR
directed
chemoproteomics
experiments
reveal
overlap
system,
capturing
subset
identified
by
SOG
system.
Finally,
deploy
our
characterization
resected
human
glioblastoma
(GBM)
tissue
samples
removed
from
locations
same
tumor,
representing
tumor's
infiltrating
edge
its
viable
center,
identifying
several
GBM
specific
interacting
proteins
may
serve
launch
point
future
therapeutic
campaigns.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(18), P. 3929 - 3934
Published: April 26, 2024
[5,15-Bis(pentafluorophenyl)-10,20-diphenylporphinato]zinc(II)
(1),
a
metalloporphyrin
derivative
that
was
recently
reported
as
an
efficient
photocatalyst
driven
by
blue
LEDs
our
group,
found
to
catalyze
red-light-promoted
(630
nm
LEDs)
radical
cascade
reaction
of
N-3-arylpropionyloxyphthalimides
with
radicophiles
including
electron-deficient
alkenes
and
alkynes,
providing
access
range
functionalized
tetralin
dialin
derivatives.
The
catalyzed
1
took
place
via
oxidative
quenching
cycle
in
DMSO,
where
no
sacrificial
electron
donor
required,
uncovering
unique
solvent
effect
capable
promoting
the
porphyrin
catalysis.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(8), P. 5481 - 5490
Published: March 28, 2024
In
recent
years,
many
methods
for
the
synthesis
of
bicyclo[1.1.1]pentane
(BCP)
scaffolds
have
been
successfully
established
owing
to
their
remarkable
potent
bioactive
properties.
These
BCP
are
typically
derived
from
single
strain
release
[1.1.1]propellane.
However,
approaches
dual
[1.1.1]propellane
remain
elusive,
despite
potential
create
innovative
opportunities
useful
propellane
derivatization.
this
report,
we
present
herein
an
efficient
method
photocatalyzed
with
diazo
compounds.
Many
compounds,
including
those
natural
products,
such
as
(+)-borneol,
estrone,
vitamin
E,
L-menthol,
metronidazole,
and
geraniol,
can
be
applied
these
transformations.
Importantly,
allows
cleavage
formation
multiple
C–C
bonds
in
a
tandem
intersystem
crossing
(ISC)/radical
ring-opening/radical–radical
recombination
process,
products
easily
transformed
into
synthetically
challenging
spiro
[2.3]
[3.4]
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 26, 2025
Synthetic
methods
that
provide
access
to
skeletally
diverse
heterocyclic
motifs
are
poised
accelerate
drug
discovery
and
streamline
the
synthesis
of
advanced
intermediates
materials.
However,
development
such
synthetic
necessitates
leveraging
previously
unexplored
mechanistic
pathways.
We
report
herein
an
efficient
blue
light-emitting
diode
light-induced
reaction
vinyldiazoacetates
quinones
produces
spirocyclic
dihydrofurans,
featuring
synthetically
challenging
oxaspiro[4,5]decane
core
numerous
medicinal
agents,
agrochemicals,
natural
products.
In
a
departure
from
well-established
photochemical
reactivity
diazo
compounds,
these
reactions
do
not
involve
vinylcarbene
formed
by
photolytic
dinitrogen
extrusion.
Instead,
they
result
photoexcitation
quinone
its
triplet
state
with
subsequent
energy
transfer
vinyldiazo
ester.
The
addition
vinylogous
carbon
vinyldiazoacetate
oxygen
affords
diradical
collapses
dihydrofuran
upon
loss
dinitrogen.
A
strain
release-driven
Bro̷nsted
acid-catalyzed
rearrangement
products
unravels
fused
bicyclic
ring
system
equally
medicinally
valuable
chromenes,
enabling
facile
skeletal
diversification
important
motifs.
A
one-pot
conversion
of
alkyl
azides
to
diazo
compounds
is
outlined.
After
azido
group
protection
α-azidocarbonyl
compounds,
treatment
the
resulting
phosphazides
with
silica
gel
in
a
wet
solvent
afforded
α-diazo
carbonyl
products
by
azide-deprotective
conversion.
Competitive
reactions
α-azido
amides
and
aryl
demonstrate
azide-site
selectivity.
Azide-site
selective
click
functionalization
this
sequence
also
demonstrated
diazido
compounds.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(12), P. 2409 - 2413
Published: March 19, 2024
A
one-pot
conversion
of
alkyl
azides
to
diazo
compounds
is
outlined.
After
the
reaction
α-azidocarbonyl
with
Amphos,
treatment
resulting
phosphazides
silica
gel
in
a
wet
solvent
afforded
α-diazo
carbonyl
products.
Through
azido
group
protection
property
inter-
and
intramolecular
azide-site
selective
reactions
protection,
click
functionalization,
deprotection
have
been
demonstrated
one
pot.
