Organic Process Research & Development,
Год журнала:
2024,
Номер
28(11), С. 4156 - 4162
Опубликована: Окт. 30, 2024
A
novel
visible-light-induced
hydrodesulfurization
of
a
thioacetal
was
developed.
The
reaction
operates
under
mild
conditions
using
user-friendly
tris(trimethylsilyl)silane
as
the
reductant
and
low
catalyst
loading
photoactive
4CzIPN.
expansion
scope
thwarted
by
operationally
hazardous
nature
process,
occasionally
producing
fire.
Careful
examination
mixtures
allowed
to
identify
silane
(SiH4)
likely
culprit
causing
pyrophoricity.
Abstract
Visible‐light‐activated
organic
reactions
unlock
novel
avenues
for
complex
molecular
transformations,
impossible
under
standard
“thermal”
conditions,
which
makes
them
powerful
tools
in
the
arsenal
of
synthetic
chemistry.
However,
transition
metal‐based
or
photoredox
catalysts
are
often
used
to
ensure
productive
absorption
visible
light,
might
be
not
desirable
medicinal
chemistry
and
industry
due
toxicity,
low
sustainability,
high
cost
most
photocatalysts.
A
more
environmentally
economically
benign
approach
is
based
on
formation
transient
electron
donor‐acceptor
(EDA)
complexes
between
two
reagents
a
reagent
an
additive,
that
readily
absorb
acting
as
internal
photosensitizers.
Within
EDA
complex‐based
arylation
strategies,
chemical
transformations
mediated
by
noncovalent
interaction
molecules,
namely
electron‐poor
aryl
halides
their
equivalents
electron‐rich
nucleophilic
additives.
Moreover,
besides
stoichiometric
organocatalysis
can
achieved
certain
cases
through
regeneration
donor
molecules
course
reaction.
Photoexcitation
induces
single
transfer
(SET)
process
generate
radical
species
step.
This
Review
will
focus
state‐of‐the‐art
strategies
utilizing
halides,
aryldiazonium,
diaryliodonium,
arylsulfonium
arylphosphonium
salts
reactants,
published
mainly
last
five
years.
Organic Letters,
Год журнала:
2024,
Номер
26(7), С. 1495 - 1500
Опубликована: Фев. 9, 2024
Herein,
we
disclose
a
radical
desulfurative
C–C
coupling
protocol
for
the
synthesis
of
4-alkylpyridines.
A
variety
substituents
on
both
benzyl
thiols
and
4-cyanopyridines
are
tolerated.
The
reaction
is
carried
out
under
mild
photocatalyst-
transition-metal-free
conditions.
Preliminary
mechanistic
studies
show
that
an
electron
donor–acceptor
complex
formed
between
alkaline
Then,
1°,
2°,
3°
C(sp3)-centered
radicals
was
by
cleavage
C–S
bond,
4-alkylpyridines
were
achieved
through
radical–radical
with
pyridyl
anion.
Abstract
Sulfonium
salts
are
typically
bench‐stable
and
readily
available
reagents
that
showcase
diverse
chemical
reactivities.
Owing
to
these
synthetically
valuable
features,
sulfonium
salt
chemistry
has
witnessed
considerable
momentum
over
the
past
decades.
Particularly,
merger
of
electrosynthesis
enabled
utilization
electric
current
in
place
cost‐intensive
hazardous
redox
agents
maximize
attractive
characteristics
salts.
Additionally,
electrochemistry
allowed
chemists
dial
desired
potential,
offering
selective
access
target
products
otherwise
unattainable
by
either
thermal
or
photochemical
manifolds.
These
advantages
led
major
advances
chemistry.
Thus,
we,
herein,
provide
an
overview
early
pioneering
findings
recent
progress
devoted
organic
associated
with
until
December
2024,
aiming
stimulate
future
this
rapidly
evolving
arena.
The Journal of Physical Chemistry C,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 30, 2025
Desulfurization
represents
an
important
process
in
chemical
synthesis
that
produces
new
molecules
and
accesses
useful
carbon
radicals.
Photocatalytically
driving
the
reactions
under
broadband
visible
light
illumination
is
still
challenging
due
to
high
cost
of
noble
metal
complex
photocatalysts
controlled
inert
atmospheres
widely
used
reported
methods.
This
work
uses
partially
oxidized
TiN
nanoparticles
comprising
earth-abundant
elements
as
drive
desulfurization
methyl
thioglycolate
ambient
atmosphere
with
a
LED
lamp.
The
yield
product,
acetate,
up
73%
after
reaction
for
18
h.
generation
accessible
radicals
confirmed
by
forming
C–C
coupling
products
styrene.
results
shed
on
promise
modified
nanoparticles,
which
possess
strong
optical
absorption
originating
from
localized
surface
plasmon
resonances
(LSPRs),
facilitate
using
light.
Chemical Science,
Год журнала:
2024,
Номер
15(25), С. 9612 - 9619
Опубликована: Янв. 1, 2024
Herein,
we
report
a
peptide
cyclisation
strategy
via
intramolecular
interception
of
cysteine
desulfurisation.
This
method
enables
the
unprotected
peptides
in
aqueous
solution
installation
hydrocarbon
linkage.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(68)
Опубликована: Июль 16, 2024
We
have
studied
2-(2-aminophenyl)benzothiazole
and
related
derivatives
for
their
photophysical
properties
in
view
of
employing
them
as
new
readily
tunable
organic
photocatalysts.
Their
triplet
energies
were
estimated
by
DFT
calculations
to
be
the
range
52-57
kcal
mol-1,
suggesting
suitability
[2+2]
photocycloaddition
unsaturated
acyl
imidazoles
with
styrene
derivatives.
Experimental
studies
shown
that
2-(2-aminophenyl)benzothiazoles
comprising
alkylamino
groups
(NHMe,
NHiPr)
or
native
amino
group
provide
best
photocatalytic
results
these
visible-light
mediated
reactions
without
need
any
additives,
yielding
a
cyclobutane
A
combined
experimental
theoretical
approach
has
provided
insights
into
underlying
triplet-triplet
energy
transfer
process.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(17), С. 8521 - 8545
Опубликована: Янв. 1, 2024
Methods
enabling
the
dechalcogenation
of
thiols
or
selenols
have
been
investigated
and
developed
for
a
long
time
in
fields
research
as
diverse
study
prebiotic
chemistry,
engineering
fuel
processing
techniques,
biomolecule
structures
function
chemical
synthesis
biomolecules.
The
thiol
selenol
amino
acids
is
nowadays
particularly
flourishing
area
being
pillar
modern
protein
synthesis,
when
used
combination
with
selenol-based
chemoselective
peptide
ligation
chemistries.
This
review
offers
comprehensive
scholarly
overview
field,
emphasizing
emerging
trends
providing
detailed
critical
mechanistic
discussion
methods
so
far.
Taking
advantage
recently
published
reports,
it
also
clarifies
some
unexpected
desulfurization
reactions
that
were
observed
past
which
no
explanation
was
provided
at
time.
Additionally,
includes
on
principal
within
framework
newly
introduced
green
chemistry
metrics
toolkits,
well-rounded
exploration
subject.
Unnatural
amino
acids
(UAAs)
are
highly
valuable
molecules
in
organic
synthesis,
pharmaceutical
sciences,
and
material
science.
Herein,
we
present
a
photocatalytic
radical
approach
for
desulfurative
alkylation
of
cysteine
derivatives
with
arenethiol
as
the
hydrogen
atom
transfer
catalyst
making
UAAs
peptides.
The
formate
salt,
acting
donor,
situ
generates
reductive
CO
