The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 31, 2025
The
hydrodecarboxylation
of
carboxylic
acids
is
a
fundamental
functional
group
transformation
in
chemistry.
However,
current
methods
rely
on
acid
preactivation,
expensive
photocatalysts,
or
transition-metal
catalysts.
Herein,
we
describe
an
unprecedented
transition-metal-
and
photocatalyst-free
chemoselective
via
N-hydroxyphthalimide-mediated
hydrogen
atom
transfer.
This
mild
method
exhibits
broad
tolerance
enables
the
conversion
primary,
secondary,
tertiary
to
alkanes.
versatility
this
demonstrated
through
late-stage
functionalization
complex
natural
products
pharmaceuticals.
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:
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.
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).
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.
