ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(15)
Published: March 15, 2024
Abstract
Low‐valent
chromium
catalysts
are
cheap
and
less
toxic
compared
to
other
transition
metal
catalysts.
Here
in,
we
reported
a
ligand‐free
chromium(III)‐catalyzed
manganese
reductive
cross‐coupling
of
unactivated
alkyl
electrophiles,
such
as
sulfonates
chlorides,
with
trisulfide
dioxides
thiolation
agents
form
carbon−sulfur
bonds.
The
powerful
method
featured
ample
substrate
scope
wide
functional
group
tolerance,
constructing
large
number
unsymmetrical
disulfides
under
simple
conditions.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: May 27, 2024
Abstract
Herein,
we
disclose
a
highly
efficient
cobalt-catalyzed
cross-electrophile
alkynylation
of
broad
range
unactivated
chlorosilanes
with
alkynyl
sulfides
as
stable
and
practical
electrophiles.
Strategically,
employing
easily
synthesized
precursors
allows
access
to
various
alkynylsilanes
in
good
excellent
yields.
Notably,
this
method
avoids
the
utilization
strong
bases,
noble
metal
catalysts,
high
temperature
forcing
reaction
conditions,
thus
presenting
apparent
advantages,
such
substrate
scope
(72
examples,
up
97%
yield),
Csp-S
chemo-selectivity
functional
group
compatibility
(Ar-X,
X
=
Cl,
Br,
I,
OTf,
OTs).
Moreover,
utilities
are
also
illustrated
by
downstream
transformations
late-stage
modification
structurally
complex
natural
products
pharmaceuticals.
Mechanistic
studies
elucidated
that
cobalt
catalyst
initially
reacted
sulfides,
activation
occurred
via
an
S
N
2
process
instead
radical
pathway.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 31, 2025
A
formal
deoxygenative
silylation
of
primary
alcohols
is
reported.
The
one-pot
procedure
consists
an
in
situ
bromination
the
alcohol
and
a
subsequent
nickel-catalyzed
cross-electrophile
coupling
formed
alkyl
bromide
various
vinyl-substituted
chlorosilanes.
key
to
success
compatibility
nickel
catalysis
as
well
chlorosilane
electrophile
with
byproducts
preceding
step,
especially
triphenylphosphine
oxide
likely
acting
weak
ligand
for
excess
catalyst
used.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 7, 2025
Herein,
we
report
a
catalytic
reductive
[4+1]
sila-cycloaddition
between
functionalized
1,3-dienes
and
chemical
feedstock
di-,
tri-,
tetrachlorosilane(s),
enabled
by
cost-effective
pyridine-diimine-nickel
complex,
providing
practical
method
to
prepare
diverse
silacyclopent-3-enes
in
up
92%
yield,
including
bridged
spiro
silacarbocycles.
This
reaction
demonstrates
broad
substrate
compatibility,
with
different
substitution
patterns
more
accessible
E/Z
isomeric
mixture.
Notably,
trichlorosilanes
undergo
tandem
sila-cycloadditions/nucleophilic
substitutions,
while
tetrachlorosilane
successfully
performs
double
sila-cycloadditions
2
equiv
of
directly
construct
Chemical Synthesis,
Journal Year:
2025,
Volume and Issue:
5(3)
Published: April 9, 2025
Nickel-catalyzed
cross-electrophile
coupling
of
carbon-electrophiles
and
silicon-electrophiles
has
recently
emerged
as
a
powerful
tool
for
C–Si
bond
formations
to
synthesize
highly
valuable
organosilanes.
This
reductive
strategy
eliminates
the
manipulation
reactive
organometallic
reagents,
thereby
leading
good
functional
group
tolerance
high
step
economy.
However,
reported
couplings
have
use
stoichiometric
amounts
Zn
or
Mn
dust
reductant,
which
somehow
limits
synthetic
application.
Herein,
we
novel
aryl
halides
with
chlorosilanes
enabled
by
dual
photoredox/nickel
catalysis.
Instead
using
metallic
reductants,
mild
readily
available
α
-silylamine
is
selected
reliable
organic
reductant.
Various
vinyl
chlorohydrosilanes
were
coupled
smoothly.
new
catalytic
protocol
offers
an
alternative
approach
facile
synthesis
α-Alkoxyalkyl
radicals
are
generated
from
acetals
by
chromium
catalysis.
The
addition
of
the
to
α-trifluoromethyl
alkenes,
followed
β-fluoride
elimination,
efficiently
produces
gem
-difluoroalkenes
with
a
homoallylic
alkoxy
group.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(29), P. 11428 - 11434
Published: Jan. 1, 2024
The
mild
generation
of
ketyl
radicals
and
coupling
with
alkynes
are
enabled
by
cost-effective
chromium
catalysis.
It
provides
a
valuable
strategy
to
form
E
-exocyclic
allyl
alcohols
high
stereoselectivity
good
functional
group
tolerance.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(14), P. 10379 - 10383
Published: June 26, 2024
Herein
we
present
a
catalytic
cross-coupling
strategy
between
C-radicals
and
Si-radicals,
enabling
the
efficient,
gentle,
versatile
synthesis
of
dibenzylic
silanes
from
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(29), P. 6125 - 6129
Published: July 12, 2024
The
reductive
C-Si
coupling
of
chlorosilanes
offers
efficient
access
to
organosilanes,
but
its
potential
for
constructing
aliphatic
ones
remains
largely
unexplored.
This
manuscript
presents
a
nickel-catalyzed
Csp
