Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(6), P. 1442 - 1447
Published: Jan. 24, 2024
Abstract
Silylzinc
reagents
are
desirable
for
the
synthesis
of
organosilanes
due
to
their
compatibility
with
functional
groups;
however,
use
pyrophoric
silyllithium
and
dissolved
lithium
salts
in
production
hinders
development.
Our
solid
Me
3
SiZnI
circumvents
these
limitations,
herein,
we
demonstrate
its
significance
aryl
alkyl
trimethylsilanes
via
cross‐coupling
bromides.
The
milder
reaction
condition
tolerates
groups
such
as
MOM,
Boc,
Bpin,
aldehydes.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(24), P. 13008 - 13014
Published: June 7, 2023
Transition-metal-catalyzed
sila-cycloaddition
has
been
a
promising
tool
for
accessing
silacarbocycle
derivatives,
but
the
approach
limited
to
selection
of
well-defined
sila-synthons.
Herein,
we
demonstrate
potential
chlorosilanes,
which
are
industrial
feedstock
chemicals,
this
type
reaction
under
reductive
nickel
catalysis.
This
work
extends
scope
coupling
from
carbocycle
synthesis
and
single
C-Si
bond
formation
reactions.
The
proceeds
mild
conditions
shows
good
substrate
functionality
tolerance,
it
offers
new
access
silacyclopent-3-enes
spiro
silacarbocycles.
optical
properties
several
dithienosiloles
as
well
structural
variations
products
demonstrated.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(33)
Published: June 13, 2023
Abstract
The
difunctionalization
of
unsaturated
bonds
plays
a
vital
role
in
the
enrichment
molecular
complexity.
While
various
catalytic
methods
for
alkene
and
alkyne
have
been
developed
recent
years,
hetero‐functionalization
introduction
two
different
atoms
has
less
explored.
This
is
mainly
due
to
challenges
associated
with
achieving
high
chemo‐,
regio‐,
stereoselectivity,
especially
when
adding
similar
from
same
group
across
bonds.
In
this
study,
we
describe
nickel‐catalyzed,
three‐component
reductive
protocol
14
element
hetero‐difunctionalization
1,3‐enynes
using
electrochemistry.
new
method
mild,
selective,
general,
allowing
silyl‐,
germanyl‐,
stannyl‐alkylation
enynes.
Various
chlorosilanes
as
well
chlorogermans,
chlorostannanes
can
be
successfully
used
combination
aryl/alkyl‐substituted
primary,
secondary,
tertiary
alkyl
bromides
electroreductive
coupling.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(7), P. 4510 - 4522
Published: March 12, 2024
Organosilicons
are
privileged
skeletons
in
the
domains
of
pharmaceutical
chemistry,
organic
synthesis,
and
materials
science.
Hence,
investigating
catalytic
techniques
for
synthesis
organosilicon
compounds
has
received
a
great
deal
emphasis.
Carbosilylation
alkenes
is
an
efficient
technique
to
introduce
diverse
molecular
architectures
containing
silicon
into
chemical
space.
However,
organohalides
pseudohalides
prerequisites
most
existing
carbosilylation
protocols.
On
other
hand,
utilization
C–H
activation
been
sowing
seeds
successful
development
intricate
scaffolds.
In
this
regard,
synthetic
accessibility
complexed
derivatives
by
through
meta-C–H
approach
remained
intangible.
Herein,
we
present
three-component
strategy
arylsilylation
olefins
with
(het)arenes
silanes
integrating
iron-catalyzed
silyl
radical
generation,
coupled
intrinsic
reactivity
alkene,
ruthenium-catalyzed
functionalization
(het)arene,
leading
targeted
cross-coupled
carbosilylated
product.
addition,
theoretical
investigations
state-of-the-art
dispersion
corrected
density
functional
theory
at
B3PW91-D3/Def2TZVP/CPCM(PhCF3)
shed
intriguing
insights
on
selectivity
probable
mechanistic
pathway
underexplored
cooperative
3d/4d
transition
metal
catalysis,
such
as
formation
its
addition
alkene
catalyzed
iron,
followed
meta-selective
ruthenium
bound
arene,
furnishing
C4
substituted
(het)arene
functionalized
compounds.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(4)
Published: Nov. 26, 2022
Abstract
Catalytic,
three‐component,
cross‐electrophile
reactions
have
recently
emerged
as
a
promising
tool
for
molecular
diversification,
but
studies
focused
mainly
on
the
alkyl‐carbonations
of
alkenes.
Herein,
scope
this
method
has
been
extended
to
conjugated
dienes
and
silicon
chemistry
through
silylative
difunctionalization
1,3‐dienes
with
chlorosilanes
aryl
bromides.
The
reaction
proceeds
under
mild
conditions
afford
1,2‐linear‐silylated
products,
selectivity
that
is
different
those
obtained
from
conventional
methods
via
an
intermediary
H(C)‐η
3
‐π‐allylmetal
species.
Preliminary
mechanistic
reveal
chlorosilane
reacts
1,3‐diene
first
then
couples
bromide.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(20), P. 7707 - 7713
Published: Jan. 1, 2024
By
leveraging
the
synergistic
interplay
between
nickel
and
photoredox
catalysis,
we
have
developed
a
three-component
silylacylation
strategy
for
various
acrylates,
yielding
valuable
building
blocks
with
carbonyl
silicon
functionalities.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(39), P. 7145 - 7150
Published: Sept. 22, 2022
Herein,
we
report
light-promoted
photo/hydrogen
atom
transfer
dual
catalysis
for
arylsilylation
of
alkenes
via
the
radical-radical
cross-coupling
with
diverse
hydrosilanes,
which
provides
a
simple
and
efficient
method
to
prepare
various
organosilicon
compounds
wide
range
substrate
scope
good
functional
group
tolerance
under
transition-metal-
chemical-oxidant-free
conditions.
Furthermore,
can
also
proceed
possible
electron
donor-acceptor
complex
exogenous
photocatalyst-free
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: Nov. 19, 2022
Abstract
Transition-metal
catalyzed
carbosilylation
of
alkenes
using
carbon
electrophiles
and
silylmetal
(-B,
-Zn)
reagents
as
the
nucleophiles
offers
a
powerful
strategy
for
synthesizing
organosilicones,
by
incorporating
silyl
groups
across
on
C-C
double
bonds
in
one
step.
However,
to
best
our
knowledge,
study
silylative
difunctionalization
based
remains
underdeveloped.
Herein,
we
present
an
example
alkylation
activated
olefins
with
unactivated
alkyl
bromides
chlorosilanes
under
nickel
catalysis.
The
main
feature
this
protocol
is
employing
more
easily
accessible
substrates
including
primary,
secondary
tertiary
bromides,
well
various
without
pre-generated
organometallics.
A
wide
range
alkylsilanes
diverse
structures
can
be
efficiently
assembled
single
step,
highlighting
good
functionality
tolerance
approach.
Furthermore,
successful
functionalization
bioactive
molecules
synthetic
applications
method
demonstrate
its
practicability.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: March 15, 2023
Facile
formation
of
carbon-heteroatom
bonds
is
a
long-standing
objective
in
synthetic
organic
chemistry.
However,
direct
cross-coupling
with
readily
accessible
alkenyl
acetates
via
inert
C‒O
bond-cleavage
for
the
bond
construction
remains
challenging.
Here
we
report
practical
preparation
stereoselective
tri-
and
tetrasubstituted
silanes
stannanes
by
performing
cobalt-catalyzed
silylation
stannylation
using
silylzinc
pivalate
stannylzinc
chloride
as
nucleophiles.
This
protocol
features
complete
control
chemoselectivity,
stereoselectivity,
well
excellent
functional
group
compatibility.
The
resulting
show
high
reactivities
arylation
alkenylation
Hiyama
Stille
reactions.
utility
further
illustrated
facile
late-stage
modifications
natural
products
drug-like
molecules.
Mechanistic
studies
suggest
that
reaction
might
involve
chelation-assisted
oxidative
insertion
cobalt
species
to
bond.
We
anticipate
our
findings
should
prove
instrumental
potential
applications
this
technology
syntheses
drug
discoveries
medicinal
