Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 29, 2024
Abstract
Photomediated
Atom
Transfer
Radical
Polymerization
(photoATRP)
is
an
activator
regeneration
method,
which
allows
for
the
controlled
synthesis
of
well‐defined
polymers
via
light
irradiation.
Traditional
photoATRP
often
limited
by
need
high‐energy
ultraviolet
or
violet
light.
These
could
negatively
affect
control
and
selectivity
polymerization,
promote
side
reactions,
may
not
be
applicable
to
biologically
relevant
systems.
This
drawback
can
circumvented
introduction
catalytic
amount
photocatalysts,
absorb
visible
and/or
NIR
and,
therefore,
controlled,
regenerative
ATRP
performed
with
dual‐catalytic
cycle.
Herein,
a
critical
summary
recent
developments
in
field
dual‐catalysis
concerning
Cu‐catalyzed
provided.
Contributions
involved
species
are
examined
mechanistically,
followed
challenges
future
directions
towards
next
generation
advanced
functional
macromolecular
materials.
Organic Letters,
Год журнала:
2024,
Номер
26(11), С. 2271 - 2275
Опубликована: Март 8, 2024
A
clean
and
direct
three-component
radical
1,2-difunctionalization
of
various
alkenes
with
perfluoroalkyl
iodides
thiosulfonates
enabled
by
the
electron
donor–acceptor
complex
has
been
developed
under
light
illumination
at
room
temperature.
The
approach
offers
a
convenient
environmentally
friendly
route
for
simultaneous
incorporation
Csp3–Rf
Csp3–S
bonds,
affording
valuable
polyfunctionalized
alkane
derivatives
containing
fluorine
sulfur
in
satisfactory
yields.
Consequently,
this
methodology
holds
significant
value
practicality
field
organic
synthesis.
Abstract
Thiols
constitute
an
important
family
among
sulfur‐containing
compounds,
with
well‐established
applications
in
various
fields
ranging
from
medicine
to
material
science.
For
instance,
thiol
residues
are
good
hydrogen
donors
which
reduce
radical
species
biological
or
chemical
processes.
However,
even
though
the
S−H
bond
activation
of
thiols
for
providing
access
thiyl
radicals
has
been
largely
studied,
desulfurative
processes
affording
carbon‐based
by
C−S
have
less
explored.
In
recent
years,
photoredox
catalysis
become
prevalent
method
generation
under
soft
reaction
conditions
readily
available
starting
materials
visible
light.
this
context,
studies
devoted
development
photocatalytic
procedures
aiming
at
desulfurization
derivatives
leading
new
C−H,
C−C
C‐Het
formation
reactions.
This
review
will
cover
synthetic
methodologies
and
strategies
photo‐mediated
native
thiols,
thioethers,
sulfonium
salts
xanthates
organic
compounds.
emerging
field
is
especially
interesting
transformations
cysteine
peptide
derivatives.
Chemical Communications,
Год журнала:
2023,
Номер
59(75), С. 11196 - 11199
Опубликована: Янв. 1, 2023
A
visible
light-driven
di-functionalization
of
maleimide
with
disulfide
and
in
situ
-generated
singlet
oxygen
offers
selective
1,2-thiohydroxylation
under
additive-free
conditions.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 29, 2024
Abstract
Photomediated
Atom
Transfer
Radical
Polymerization
(photoATRP)
is
an
activator
regeneration
method,
which
allows
for
the
controlled
synthesis
of
well‐defined
polymers
via
light
irradiation.
Traditional
photoATRP
often
limited
by
need
high‐energy
ultraviolet
or
violet
light.
These
could
negatively
affect
control
and
selectivity
polymerization,
promote
side
reactions,
may
not
be
applicable
to
biologically
relevant
systems.
This
drawback
can
circumvented
introduction
catalytic
amount
photocatalysts,
absorb
visible
and/or
NIR
and,
therefore,
controlled,
regenerative
ATRP
performed
with
dual‐catalytic
cycle.
Herein,
a
critical
summary
recent
developments
in
field
dual‐catalysis
concerning
Cu‐catalyzed
provided.
Contributions
involved
species
are
examined
mechanistically,
followed
challenges
future
directions
towards
next
generation
advanced
functional
macromolecular
materials.
Molecules
containing
fluoroalkyl
and
arylthio
groups
play
a
pivotal
role
in
pharmaceutical
agrochemical
development.
The
simultaneous
introduction
of
these
functional
through
the
1,2-difunctionalization
alkenes
is
an
efficient
strategy.
Fluoroalkyl
phenyl
sulfones
serve
as
accessible
radical
precursors;
however,
their
tendency
to
interact
with
thiophenol
via
electron
donor–acceptor
interaction
mechanism
can
impede
desired
transformation.
Through
meticulous
selection
solvent
base,
we
successfully
utilized
copper
catalysis
facilitate
alkene-involved
three-component
reaction.
Our
work
unveils
photoredox
copper-catalyzed
fluoroalkylation–thiolation
using
various
(such
perfluoroethyl,
tetrafluoroethyl,
trifluoromethyl,
difluoromethyl,
difluoroalkyl,
difluorobenzyl).
efficacy
this
approach
exemplified
by
synthesis
Kengreal
derivatives.
A
TBHP-promoted
trifluoromethyl-difluoromethylthiolation
of
alkenes
was
reported.
Langlois'
reagent
used
as
a
stable
and
inexpensive
trifluoromethyl
source.
In
the
presence
TBHP,
radical
generated
reacted
with
alkenes,
achieving
new
alkyl
radical,
which
could
be
trapped
by
PhSO2SCF2H,
forming
C-C
C-S
bonds
in
one
step
incorporating
difluoromethylthio
groups.
The
mild
conditions
broad
functional
group
tolerance
endowed
reaction
great
potential
field
pharmaceuticals
agrochemicals.
Chemical Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
Dual
ligand-enabled
iron
photocatalysis
for
the
conversion
of
all
kinds
halogen-containing
carboxylates
(C
n
X
m
COO
−
,
X:
F,
Cl,
Br)
to
C
radicals
is
disclosed
chloro/fluoro-polyhaloalkylation
non-activated
alkenes.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(17), С. 4762 - 4768
Опубликована: Янв. 1, 2024
A
method
for
the
generation
of
hexafluoroisopropyl
radical
by
photoredox
cleavage
C,O
bond
is
described.
The
key
reagent
obtained
from
hexafluoroisopropanol.
