Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(24)
Published: March 28, 2022
A
regioselective
addition
of
alkynylsilanes
across
unactivated,
terminal
alkenes
is
reported.
The
reaction
initiated
by
the
capture
a
sterically
unhindered
silylium
ion
silylated
phenylacetylene
derivative
to
form
bis(silylated)
ketene-like
carbocation.
This
in
situ-generated
key
intermediate
actual
catalyst
that
maintains
catalytic
cycle
series
electrophilic
reactions
ions
and
β-silicon-stabilized
carbocations.
computed
mechanism
fully
consistent
with
experimental
findings.
unprecedented
two-component
carbosilylation
establishes
C(sp
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(13), P. 7804 - 7810
Published: June 16, 2022
A
visible-light-driven
silyl
radical
generation
method
from
silylboronates
has
been
developed.
The
activation
of
with
a
catalytic
amount
mild
base
promoted
the
single-electron
oxidation
process
to
form
radicals.
Facile
single
electron
transfer
for
borate
readily
occurred
without
hydrogen
atom
hydrosilane
in
presence
various
photoredox
catalysts.
Combining
this
protocol
radical-mediated
N-heterocyclic
carbene
catalysis
enabled
acylsilylation
alkenes
via
relay
generation.
Furthermore,
recent
advanced
methods
synthesis
significantly
improved
utility
process.
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.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(5), P. 1011 - 1016
Published: Jan. 30, 2024
A
novel
strategy
was
developed
to
generate
silyl
radicals
from
silylboronic
pinacol
esters
(SPEs)
through
nucleohomolytic
substitution
of
boron
with
aminyl
radicals.
We
successfully
applied
this
obtain
diverse
organosilicon
compounds
using
SPEs
and
N-nitrosamines
under
photoirradiation
without
any
catalyst.
The
ability
access
offers
a
new
perspective
for
chemists
rapidly
construct
Si–X
bonds.
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.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
27(2), P. 680 - 685
Published: Jan. 6, 2025
The
efficient
construction
of
chiral
aryl-containing
organosilicon
frameworks
via
catalytic
enantioselective
three-component
silylarylation
alkenes
remains
a
great
challenge.
Herein,
photoredox/nickel
dual-catalytic
asymmetric
protocol
has
been
disclosed
by
using
biimidazoline
(BiIM)
as
the
ligand,
silylboranes
silyl
radical
precursors,
aryl
bromides
coupling
partners,
and
morpholine
promoter.
Remarkably,
reaction
features
mild
green
conditions,
high
efficiency,
excellent
enantioselectivity,
enabling
facile
synthesis
valuable
tropic
acid
sila-isoflavanone
structures.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(22), P. 4019 - 4023
Published: May 25, 2022
Herein,
we
report
a
direct,
light-mediated
defluorosilylation
protocol
for
converting
α-trifluoromethyl
arylalkenes
and
alkyl
silanes
into
γ,γ-difluoroallylic
compounds
via
combination
of
photoredox
catalysis
hydrogen
atom
transfer.
The
clean,
convenient
can
be
scaled
to
the
gram
level,
its
mild
conditions
make
it
very
suitable
late-stage
functionalization
complex
natural
products
drugs.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(8), P. 4785 - 4791
Published: Jan. 1, 2024
We
have
developed
an
efficient
photocatalyzed
arylsilylation
of
alkenes,
utilizing
silylboranes
and
(hetero)aryl
nitriles
in
the
presence
base
photocatalyst.
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.
