Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(32)
Published: May 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
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(21)
Published: April 7, 2023
Abstract
The
exceptional
versatility
of
carboxylic
acids
has
been
extensively
exploited
in
organic
synthesis
across
several
decades.
There
a
recent
upsurge
radical
decarboxylative
transformations.
process
can
be
initiated
under
mild
conditions,
and
the
resultant
radicals
have
orthogonal
reactivities
to
closed‐shell
species,
thus
providing
immense
opportunities
for
streamlining
novel
reactions.
use
free
is
most
desirable
owing
its
high
atom
step
economy.
Aiming
demonstrate
attractiveness
strategy
inspire
chemists
tackle
existing
challenges,
this
review
outlines
advances
on
functionalization
acids.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(5), P. 1110 - 1115
Published: Jan. 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 Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(19), P. 4764 - 4773
Published: Jan. 1, 2023
A
photo-induced
iron-catalyzed
strategy
that
facilitates
the
transformation
of
carboxylic
acids
and
hydrocarbons
into
thioethers
sulfoxides
is
herein
reported.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(18), P. 5278 - 5305
Published: Jan. 1, 2024
This
review
summarizes
the
latest
methodological
advances
in
photocatalytic
C(sp
3
)–H
functionalization,
with
a
particular
emphasis
on
formation
of
C–P,
C–B,
C–S
bonds,
etc
.,
and
some
prominent
efforts
asymmetric
C–H
functionalization.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(12), P. 2381 - 2386
Published: March 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 Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(14), P. 4024 - 4040
Published: Jan. 1, 2024
This
review
provides
a
comprehensive
overview
of
metal
catalysis
in
photo-electrochemical
systems,
discussing
reaction
mechanisms
and
offering
prospects
for
this
triadic
catalytic
mode.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(6), P. 1729 - 1735
Published: Jan. 1, 2024
An
iron-catalyzed
fragmentation
alkynylation,
alkenylation
and
alkylation
enabled
by
photoinduced
ligand-to-metal
charge
transfer
(LMCT)processis
herein
reported.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 26, 2025
A
photoinduced
copper-mediated
acyloxylation
of
arylthianthrenium
or
arylphenoxathiinium
salts
with
either
aliphatic
aromatic
carboxylic
acids
is
described
for
the
convenient
synthesis
O-aryl
esters.
The
reaction
has
shown
obvious
advantages,
such
as
high
efficiency,
good
functional
group
tolerance,
excellent
chemoselectivity,
and
capacity
esterification
complex
drug
molecules,
offering
a
practical
synthetic
route
to
multifunctionalized
sterically
congested
esters,
which
are
potentially
useful
in
development
new
prodrugs
twin
drugs.
