ACS Catalysis,
Год журнала:
2022,
Номер
12(21), С. 13225 - 13233
Опубликована: Окт. 17, 2022
Site-selective
C–H
functionalization
of
heteroarenes
is
important
for
the
rapid
modification
bioactive
molecules.
Herein,
we
report
an
efficient
photocatalytic
platform
visible-light-mediated
alkylation
pyridines
at
C4
position
using
alkyl
carboxylic
acids
as
alkylating
agents
under
external
oxidant-free
conditions.
Importantly,
released
N-centered
radical
can
serve
effective
oxidizing
agent
single-electron
transfer
(SET)
oxidation
to
efficiently
regenerate
photocatalyst.
This
system
appealing
from
a
mechanistic
perspective
and
amenable
broad
substrate
scope
containing
oxidatively
sensitive
functionalities
that
do
not
hold
up
other
procedures.
The
strategy
offers
practical
approach
C4-selective
pyridylation
diverse
range
primary,
secondary,
tertiary
amino
with
various
functional
groups
mild,
metal-free
ACS Catalysis,
Год журнала:
2023,
Номер
13(3), С. 1678 - 1685
Опубликована: Янв. 13, 2023
We
report
a
photoinduced
iron/copper
dual-catalytic
strategy
for
the
radical
decarboxylation
functionalization
of
aliphatic
carboxylic
acids.
The
ligand-to-iron
charge
transfer
process
under
light
was
initially
occurred
to
generate
an
unstabilized
alkyl
radical,
and
copper
catalyst
delivered
enabled
subsequent
coupling
reactions
form
C–N
or
C–C
bonds.
By
merging
iron-catalyzed
with
catalysis,
this
system
allows
smooth
conversion
wide
range
acids
amination,
decarboxylative
dehydrogenation,
alkylation
efficiently.
A
variety
complex
drug
natural
molecules
is
applicable,
suggesting
that
would
facilitate
rapid
compound
library
synthesis
benefit
discovery
pharmaceutical
agents.
ACS Catalysis,
Год журнала:
2024,
Номер
14(3), С. 1300 - 1310
Опубликована: Янв. 11, 2024
Directly
utilizing
abundant
and
inexpensive
sources
of
aliphatic
carboxylic
acids
is
highly
attractive
for
the
synthesis
CF2H-
CH3-containing
compounds.
Herein,
we
report
a
versatile
photoinduced
iron-catalyzed
platform
hydrodifluoromethylation
hydromethylation
alkenes
without
need
additional
stoichiometric
oxidants.
These
two
transformations
are
accomplished
by
visible-light-induced
ligand-to-iron
charge
transfer
open-shell
activation
system
using
industrial
chemical
difluoroacetic
acetic
as
precursors
postulated
to
operate
via
difluoromethyl
methyl
radical-mediated
decarboxylation
mechanism.
Experimental
results
show
that
strategy
also
applicable
difunctionalization
unactivated
alkenes.
Meanwhile,
this
provides
viable
route
pharmaceutically
active
molecules
containing
deuterated
units.
The
protocol
exhibits
several
features,
including
mild
reaction
conditions,
divergent
radical
precursors,
operational
simplicity
scalability,
good
chemo-
regioselectivity,
scalability
supported
continuous
flow
technology,
ability
provide
high-value
building
blocks
applications
in
one
step.
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(24), С. 4189 - 4230
Опубликована: Дек. 3, 2022
Abstract
In
the
quest
for
sustainable
processes,
selection
of
resources
and
catalysts
is
central
importance.
Carboxylic
acids,
which
are
abundant,
stable
ideally
biobased
feedstocks,
can
be
considered
as
attractive
platforms
towards
a
range
functionalized
molecules.
A
recent
resurgence
photoinduced
ligand‐to‐metal
charge
transfer
(LMCT)
carboxylates
led
to
tremendous
developments
in
field
earth‐abundant
metal
mediated,
visible‐light
induced
(non)‐decarboxylative
transformations
carboxylic
acids.
These
reactions
combine
use
available
starting
materials,
low‐consuming
energy
source
abundant
catalysts.
Besides
these
undeniable
advantages,
they
also
provide
mild,
highly
selective
innovative
conditions
complex
molecule
functionalization.
The
objective
this
review
give
an
overview
advances
LMCT
with
special
focus
on
mechanistic
aspects
transformations.
magnified
image
Chemical Science,
Год журнала:
2022,
Номер
13(45), С. 13611 - 13616
Опубликована: Янв. 1, 2022
Sulfoximines
are
synthetically
important
scaffolds
and
serve
roles
in
drug
discovery.
Currently,
there
is
no
solution
to
decarboxylative
sulfoximination
of
benzoic
acids;
although
thoroughly
investigated,
limited
substrate
scope
harsh
reaction
conditions
still
hold
back
traditional
thermal
aromatic
functionalization.
Herein,
we
realize
the
first
acids
via
photo-induced
ligand
copper
charge
transfer
(copper-LMCT)-enabled
carbometalation.
The
transformation
proceeds
under
mild
conditions,
has
a
broad
scope,
can
be
applied
late-stage
functionalization
complex
small
molecules.
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.
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).
