Angewandte Chemie,
Год журнала:
2024,
Номер
136(32)
Опубликована: Май 13, 2024
Abstract
We
report
an
iron‐catalyzed
decarboxylative
C(sp
3
)−O
bond‐forming
reaction
under
mild,
base‐free
conditions
with
visible
light
irradiation.
The
transformation
uses
readily
available
and
structurally
diverse
carboxylic
acids,
iron
photocatalyst,
2,2,6,6‐tetramethylpiperidine
1‐oxyl
(TEMPO)
derivatives
as
oxygenation
reagents.
process
exhibits
a
broad
scope
in
acids
possessing
wide
range
of
stereoelectronic
properties
functional
groups.
developed
was
applied
to
late‐stage
series
bio‐active
molecules.
leverages
the
ability
complexes
generate
carbon‐centered
radicals
directly
from
by
photoinduced
carboxylate‐to‐iron
charge
transfer.
Kinetic,
electrochemical,
EPR,
UV/Vis,
HRMS,
DFT
studies
revealed
that
TEMPO
has
triple
role
reaction:
reagent,
oxidant
turn
over
Fe‐catalyst,
internal
base
for
acid
deprotonation.
obtained
adducts
represent
versatile
synthetic
intermediates
were
further
engaged
C−C
C‐heteroatom
reactions
using
commercial
organo‐photocatalysts
nucleophilic
Chemical Science,
Год журнала:
2024,
Номер
15(18), С. 6661 - 6678
Опубликована: Янв. 1, 2024
Ligand-to-metal
charge
transfer
(LMCT)
excited
states
showcase
promise
in
enabling
photochemical
reactions.
This
article
details
design
principles
to
enable
low
energy
LMCT
and
notable
examples
that
drive
reactions
from
these
states.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(5)
Опубликована: Дек. 13, 2023
Trifluoroacetates
are
the
most
abundant
and
accessible
sources
of
trifluoromethyl
groups,
which
key
components
in
pharmaceuticals
agrochemicals.
The
generation
reactive
radicals
from
trifluoroacetates
requires
their
decarboxylation,
is
hampered
by
high
oxidation
potential.
This
constitutes
a
major
challenge
for
redox-based
methods,
because
need
to
pair
redox
potentials
with
trifluoroacetate.
Here
we
report
strategy
based
on
iron
photocatalysis
promote
direct
photodecarboxylation
that
displays
reactivity
features
escape
limitations.
Our
synthetic
design
has
enabled
use
trifluoromethylation
more
easily
oxidizable
organic
substrates,
offering
new
opportunities
late-stage
derivatization
campaigns
using
chemical
feedstocks,
Earth-abundant
catalysts,
visible-light.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(19), С. 4764 - 4773
Опубликована: Янв. 1, 2023
A
photo-induced
iron-catalyzed
strategy
that
facilitates
the
transformation
of
carboxylic
acids
and
hydrocarbons
into
thioethers
sulfoxides
is
herein
reported.
Chemical Science,
Год журнала:
2023,
Номер
15(1), С. 124 - 133
Опубликована: Ноя. 24, 2023
Simple
iron
salts
are
able
to
photocatalyze
the
diazidation,
dichlorination,
and
fluorochlorination
of
alkenes
via
merger
ligand-to-metal
charge
transfer
(LMCT)
either
radical
ligand
(RLT)
or
fluorine
atom
(FAT).
Organic Letters,
Год журнала:
2023,
Номер
25(28), С. 5279 - 5284
Опубликована: Июль 11, 2023
The
synthesis
of
tertiary
phosphines(III)
has
been
a
long-standing
challenge
in
synthetic
chemistry
because
inevitable
issues
including
harsh
conditions,
sensitive
organometallic
reagents,
and
prefunctionalized
substrates
traditional
synthesis.
Herein,
we
report
strategically
novel
C(sp3)-H
bond
phosphorylation
that
enables
the
assembly
structurally
diverse
from
industrial
phosphine(III)
sources
under
mild
photocatalytic
conditions.
merger
ligand-to-metal
charge
transfer
(LMCT)
FeCl3
with
hydrogen
atom-transfer
(HAT)
process
is
key
for
generation
alkyl
radicals
hydrocarbons.
Strikingly,
this
catalytic
system
can
be
successfully
applied
polymerization
electron-deficient
alkenes.
Organic Letters,
Год журнала:
2024,
Номер
26(5), С. 1110 - 1115
Опубликована: Янв. 26, 2024
Despite
the
significant
success
of
decarboxylative
radical
reactions,
catalytic
systems
vary
considerably
upon
different
acceptors,
requiring
renewed
case-by-case
reaction
optimization.
Herein,
we
developed
an
iron
condition
that
enables
highly
efficient
decarboxylation
various
carboxylic
acids
for
a
range
transformations.
This
operationally
simple
protocol
was
amenable
to
wide
array
delivering
structurally
diverse
oxime
ethers,
alkenylation,
alkynylation,
thiolation,
and
amidation
products
in
useful
excellent
yields
(>40
examples,
up
95%
yield).
Organic Letters,
Год журнала:
2024,
Номер
26(12), С. 2381 - 2386
Опубликована: Март 15, 2024
Organic
sulfones
are
an
important
class
of
chemical
compounds
widely
used
in
many
research
fields.
The
direct
decarboxylative
sulfonylation
carboxylic
acids
is
attractive
but
challenging,
particularly
when
iron
as
a
metal
catalyst.
Herein,
we
describe
photoinduced
iron-catalytic
method
for
the
synthesis
directly
using
via
radical-based
decarboxylation.
This
protocol
mild,
highly
efficient,
and
easy-to-operate.
A
broad
scope
carbon
electrophiles
could
be
well
tolerated.
mechanism
involving
iron-catalyzed
decarboxylation,
radical
transfer,
single-electron
reduction,
nucleophilic
attack
proposed.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июль 20, 2024
Abstract
Reforming
sustainable
3d-metal-based
visible
light
catalytic
platforms
for
inert
bulk
chemical
activation
is
highly
desirable.
Herein,
we
demonstrate
the
use
of
a
Brønsted
acid
to
unlock
robust
and
practical
iron
ligand-to-metal
charge
transfer
(LMCT)
photocatalysis
multifarious
haloalkylcarboxylates
(C
n
X
m
COO
−
,
=
F
or
Cl)
produce
C
radicals.
This
process
enables
fluoro-polyhaloalkylation
non-activated
alkenes
by
combining
easily
available
Selectfluor
as
fluorine
source.
Valuable
alkyl
fluorides
including
potential
drug
molecules
can
be
obtained
through
this
protocol.
Mechanistic
studies
indicate
that
real
light-harvesting
species
may
derive
from
in
situ-assembly
Fe
3+
H
+
acetonitrile
solvent,
which
indeed
increases
efficiency
LMCT
between
center
via
hydrogen-bond
interactions.
We
anticipate
acid-unlocked
platform
would
an
intriguing
option
execute
compounds.
