Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(48)
Published: Aug. 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,
Journal Year:
2023,
Volume and Issue:
62(36)
Published: July 18, 2023
Catalytic
enantioselective
intermolecular
C-H
silylation
offers
an
efficient
approach
for
the
rapid
construction
of
chiral
organosilicon
compounds,
but
remains
a
significant
challenge.
Herein,
new
type
silyl
ligand
is
developed,
which
enables
first
iridium-catalyzed
atroposelective
reaction
2-arylisoquinolines.
This
protocol
features
mild
conditions,
high
atom
economy,
and
remarkable
yield
with
excellent
stereoselectivity
(up
to
99
%
yield,
ee),
delivering
enantioenriched
axially
silane
platform
molecules
facile
convertibility.
Key
success
this
unprecedented
transformation
relies
on
novel
PSiSi-ligand,
facilitates
process
perfect
chem-,
regio-
stereo-control
via
multi-coordinated
iridium
complex.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(17), P. 8546 - 8562
Published: Jan. 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,
Journal Year:
2024,
Volume and Issue:
63(48)
Published: Aug. 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.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(25)
Published: April 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]
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(33), P. 23092 - 23102
Published: Aug. 7, 2024
Enantiopure
Si-stereogenic
organosilanes
are
highly
valued
in
the
fields
of
organic
synthesis,
development
advanced
materials,
and
drug
discovery.
However,
they
not
naturally
occurring,
their
synthesis
has
been
largely
confined
to
resolution
racemic
silanes
or
desymmetrization
symmetric
silanes.
In
contrast,
dynamic
kinetic
asymmetric
transformation
(DYKAT)
offers
a
mechanistically
distinct
approach
would
broaden
accessibility
an
enantioconvergent
manner.
this
study,
we
report
Lewis
base-catalyzed
DYKAT
chlorosilanes.
The
chiral
isothiourea
catalyst,
(S)-benzotetramisole,
facilitates
silyletherification
with
phenols,
yielding
(R)-silylethers
good
yields
high
enantioselectivity
(27
examples,
up
86%
yield,
98:2
er).
Kinetic
analysis,
control
experiments,
DFT
calculations
suggest
that
two-catalyst-bound
pentacoordinate
silicate
is
responsible
for
Si-configurational
epimerization
ion-paired
tetracoordinated
silicon
intermediates.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(8), P. 1763 - 1769
Published: March 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.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(36)
Published: July 30, 2024
Functionalization
of
Si-bound
methyl
group
provides
an
efficient
access
to
diverse
organosilanes.
However,
the
asymmetric
construction
silicon-stereogenic
architectures
by
functionalization
has
not
yet
been
described
despite
recent
significant
progress
in
producing
chiral
silicon.
Herein,
we
disclosed
enantioselective
silylmethyl
involving
aryl
alkyl
1,5-palladium
migration
naphthalenes
possessing
enantioenriched
stereogenic
silicon
center,
which
are
inaccessible
before.
It
is
worthy
note
that
realization
induction
at
step
metal
itself
remains
challenging.
Our
study
constitutes
first
reaction.
The
key
success
discovery
and
fine-tuning
different
substituents
α,α,α,α-tetraaryl-1,3-dioxolane-4,5-dimethanol
(TADDOL)-based
phosphoramidites,
ensure
enantioselectivity
desired
reactivity.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(10), P. 1991 - 1995
Published: March 1, 2024
A
carboxylate-catalyzed,
metal-free
C-silylation
protocol
for
terminal
alkynes
is
reported
using
a
quaternary
ammonium
pivalate
as
the
catalyst
and
commercially
available
N,O-bis(silyl)acetamides
silylating
agents.
The
reaction
proceeds
under
mild
conditions,
tolerates
range
of
functionalities,
enables
concomitant
O-
or
N-silylation
acidic
OH
NH
groups.
Hammett
ρ
value
+1.4
±
0.1
obtained
para-substituted
2-arylalkynes
consistent
with
proposed
catalytic
cycle
involving
turnover-determining
deprotonation
step.
