ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(20), P. 13474 - 13483
Published: Oct. 5, 2023
The
utilization
of
sulfinyl
sulfones
in
transition-metal-catalyzed
synthetic
chemistry
has
rarely
been
investigated.
Here
we
report
the
design
and
nickel-catalytic
conversion
situ-generated
redox-active
for
reductive
coupling
with
a
wide
variety
organic
halides
by
dual-role
nickel
catalyst
reductant
Zn.
Mechanistic
studies
disclose
that
key
such
reaction
is
employment
sulfones,
enabling
situ
generation
electrophilic
sulfur
reagents
through
zinc-induced
reduction
facilitated
catalyst.
This
strategy
demonstrates
good
tolerance
range
functional
groups.
Furthermore,
this
method
extends
to
meta-substituted
diaryl
sulfides,
modification
complex
bioactive
molecules
synthesis
thioether-containing
drugs.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(19), P. 11619 - 11663
Published: Sept. 26, 2023
The
functionalization
of
C–H
bonds
in
organic
molecules
containing
functional
groups
has
been
one
the
holy
grails
catalysis.
One
synthetically
important
approach
to
diverse
is
catalytic
silylation
or
borylation
bonds,
which
enables
a
broad
array
downstream
transformations
afford
structures.
Advances
both
undirected
and
directed
methods
for
transition-metal-catalyzed
have
led
their
rapid
adoption
early-,
mid-,
late-stage
synthesis
complex
molecules.
In
this
Review,
we
review
application
bioactive
molecules,
materials,
ligands.
Overall,
aim
provide
picture
state
art
as
applied
modification
architectures
that
will
spur
further
development
these
reactions.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(3), P. 1300 - 1310
Published: Jan. 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.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 6, 2025
The
integration
of
ligand-to-metal
charge
transfer
(LMCT)
catalytic
paradigms
with
radical
intermediates
has
transformed
the
selective
functionalization
inert
C-H
bonds,
facilitating
use
nonprecious
metal
catalysts
in
demanding
transformations.
Notably,
aerobic
carbonylation
methane
to
acetic
acid
remains
formidable
due
rapid
oxidation
methyl
radicals,
producing
undesired
C1
oxygenates.
We
present
an
iron
terpyridine
catalyst
utilizing
LMCT
achieve
exceptional
C2/C1
selectivity
through
synergistic
photoexcitation,
generation,
and
carbonylation.
Mechanistic
studies
highlight
critical
roles
Fe(II)
Fe-carbonyl
complexes
bypassing
via
a
rebound-like
pathway,
unlocking
unprecedented
efficiency
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(28), P. 15207 - 15217
Published: July 6, 2023
Borylations
of
inert
carbon-hydrogen
bonds
are
highly
useful
for
transforming
feedstock
chemicals
into
versatile
organoboron
reagents.
Catalysis
these
reactions
has
historically
relied
on
precious-metal
complexes,
which
promote
dehydrogenative
borylations
with
diboron
reagents
under
oxidant-free
conditions.
Recently,
photoinduced
radical-mediated
involving
hydrogen
atom
transfer
pathways
have
emerged
as
attractive
alternatives
because
they
provide
complimentary
regioselectivities
and
proceed
metal-free
However,
net
oxidative
processes
require
stoichiometric
oxidants
therefore
cannot
compete
the
high
economy
their
precious-metal-catalyzed
counterparts.
Herein,
we
report
that
CuCl2
catalyzes
radical-mediated,
C(sp3)-H
alkanes
bis(catecholato)diboron
This
is
a
result
an
unexpected
dual
role
copper
catalyst,
promotes
oxidation
reagent
to
generate
electrophilic
bis-boryloxide
acts
effective
borylating
agent
in
subsequent
redox-neutral
photocatalytic
C-H
borylations.
