Angewandte Chemie,
Год журнала:
2024,
Номер
136(48)
Опубликована: Авг. 14, 2024
Abstract
Silacycles
have
exhibited
significant
potential
for
application
in
the
fields
of
medicinal
chemistry,
agrochemistry,
and
materials
science.
Accordingly,
development
effective
methods
synthesizing
these
compounds
has
attracted
increasing
attention.
Here,
we
report
an
efficient
Cu‐catalyzed
enantioselective
hydrosilylation
arylmethylenecyclopropanes
with
hydrosilanes,
that
allows
rapid
assembly
various
enantioenriched
carbon‐
silicon‐stereogenic
silacyclopentanes
good
yields
excellent
enantioselectivities
diastereoselectivities
under
mild
conditions.
Further
stereospecific
transformation
Si−H
bond
on
chiral
silicon
center
expands
diversity
C‐
Si‐stereogenic
silacyclopentanes.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(25)
Опубликована: Апрель 12, 2024
The
catalytic
access
of
silicon-stereogenic
organosilanes
remains
a
big
challenge,
and
largely
depends
on
the
desymmetrization
symmetric
precursors
with
two
identical
substitutes
attached
to
silicon
atom.
Here
we
report
construction
via
kinetic
resolution
racemic
monohydrosilanes
good
excellent
selectivity
factors.
Both
Si-stereogenic
dihydrobenzosiloles
could
be
efficiently
accessed
in
one
single
operation
Rh-catalyzed
enantioselective
intramolecular
hydrosilylation,
employing
(R,R)-Et-DuPhos
as
optimal
ligand.
This
protocol
features
mild
conditions,
low
catalyst
loading
(0.1
mol
%
[Rh(cod)Cl]
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(17), С. 8546 - 8562
Опубликована: Янв. 1, 2024
Silicon-stereogenic
chiral
organosilanes
have
found
increasing
applications
in
synthetic
chemistry,
medicinal
and
materials
science.
In
this
context,
various
asymmetric
catalytic
methods
been
established
for
the
diverse
synthesis
of
silicon-stereogenic
silanes.
particular,
organocatalysis
is
emerging
as
an
important
complementary
tool
enantioselective
construction
silicon-stereocenters,
along
with
rapid
development
chiral-metal
catalyzed
protocols.
Its
advent
provides
a
powerful
platform
to
achieve
functionalized
structural
diversity,
should
lead
great
organosilicon
chemistry.
Tutorial
Review,
we
highlight
these
latest
achievements
from
two
aspects:
desymmetrizations
prochiral
tetraorganosilanes
dynamic
kinetic
transformations
racemic
by
employing
five
organocatalytic
activation
modes.
The
advantages,
limitations
value
each
protocol,
well
opportunities
still
open
further
exploration,
are
also
discussed.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(48)
Опубликована: Авг. 14, 2024
Silacycles
have
exhibited
significant
potential
for
application
in
the
fields
of
medicinal
chemistry,
agrochemistry,
and
materials
science.
Accordingly,
development
effective
methods
synthesizing
these
compounds
has
attracted
increasing
attention.
Here,
we
report
an
efficient
Cu-catalyzed
enantioselective
hydrosilylation
arylmethylenecyclopropanes
with
hydrosilanes,
that
allows
rapid
assembly
various
enantioenriched
carbon-
silicon-stereogenic
silacyclopentanes
good
yields
excellent
enantioselectivities
diastereoselectivities
under
mild
conditions.
Further
stereospecific
transformation
Si-H
bond
on
chiral
silicon
center
expands
diversity
C-
Si-stereogenic
silacyclopentanes.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 3, 2025
This
study
presents
a
copper-catalyzed,
substrate-controlled
regio-
and
enantioselective
intermolecular
hydrosilylation
method
capable
of
accommodating
broad
scope
alkenes
prochiral
silanes.
The
approach
offers
an
efficient
versatile
pathway
to
generate
enantioenriched
linear
branched
alkyl-substituted
Si-stereogenic
Key
features
this
reaction
include
mild
conditions,
simple
catalytic
systems,
compatibility
with
diverse
substrates,
high
yields
enantioselectivities.
While
methods
create
chiral
carbon
centers
stereochemically
defined
silicon
have
been
developed,
the
ability
both
simultaneously
would
be
value.
Here
authors
present
substratecontrolled
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 18, 2024
Abstract
Despite
impressive
advances
in
the
construction
of
enantioenriched
silacarbocycles
featuring
silicon‐stereogenic
centers
via
a
selection
well‐defined
sila‐synthons,
development
more
convenient
and
economic
method
with
readily
available
starting
materials
is
significantly
less
explored
remains
considerable
challenge.
Herein,
we
report
first
example
copper‐catalyzed
sequential
hydrosilylation
accessible
methylenecyclopropanes
(MCPs)
primary
silanes,
affording
an
efficient
route
to
wide
range
chiral
silacyclopentanes
bearing
consecutive
silicon‐
carbon‐stereogenic
excellent
enantio‐
diastereoselectivities
(generally
≥98
%
ee,
>25
:
1
dr).
Mechanistic
studies
reveal
that
these
reactions
combine
intermolecular
ring‐opening
aryl
MCPs
intramolecular
asymmetric
resultant
Z
/
E
mixture
homoallylic
silanes.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(8), С. 1763 - 1769
Опубликована: Март 1, 2024
Abstract
The
direct
conversion
of
specific
C−H
bonds
to
C−Si
in
alkanes
or
aromatics
via
catalytic
methods
has
attracted
growing
research
interest.
Herein,
we
report
the
preparation
a
new
iridium
catalyst
supported
on
naphthyridine‐based
porous
organic
polymer
and
its
successful
application
dehydrogenative
silylation
2‐arylphenols
alcohol
hydrosilanes
access
ring‐fused
oxasilacycles.
synthetic
method
exhibits
broad
substrate
scope
good
functional
group
compatibility
while
avoiding
use
hydrogen
acceptors.
In
addition,
this
could
be
easily
recovered
from
reaction
system
reused
for
at
least
seven
times
without
apparent
deactivation.
This
provides
insights
further
design
heterogeneous
nanocatalysts
contributes
synthesis
silicon‐substituted
molecules.
