Chinese Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
43(10), P. 3367 - 3367
Published: Jan. 1, 2023
Chiral
allylsilanes,
a
versatile
linchpin,
are
widely
used
in
the
area
of
asymmetric
synthesis.Therefore,
development
efficient
methodologies
for
preparation
enantioenriched
allylsilanes
has
attracted
great
attention.Significant
advances
have
been
made
catalytic
enantioselective
chiral
by
virtue
rapid
developments
catalysis.The
construction
and
their
synthetic
applications
summarized.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(21), P. 3859 - 3863
Published: May 22, 2023
The
development
and
the
synthetic
applications
of
a
novel
class
diphosphine
ligands
(SPSiPs)
based
on
chiral
spirosilabiindane
diol
(SPSiOL)
are
presented.
Starting
from
SPSiOL,
could
be
readily
prepared
in
three
steps
with
high
efficiency.
This
features
rigid
configuration,
large
dihedral
angle,
P-M-P
long
P-P
distance.
potentials
SPSiPs
asymmetric
catalysis
have
also
been
preliminarily
disclosed.
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(7)
Published: Jan. 5, 2024
Abstract
A
Cu‐catalyzed
asymmetric
synthesis
of
silicon‐stereogenic
benzoxasiloles
has
been
realized
via
intramolecular
Si−O
coupling
[2‐(hydroxymethyl)phenyl]silanes.
Cu(I)/difluorphos
is
found
to
be
an
efficient
catalytic
system
for
enantioselective
Si−C
bond
cleavage
and
formation.
In
addition,
kinetic
resolution
racemic
substituted
[2‐(hydroxymethyl)phenyl]silanes
using
Cu(I)/
PyrOx
(pyridine‐oxazoline
ligands)
as
the
developed
afford
carbon‐
benzoxasiloles.
Ring‐opening
reactions
chiral
with
organolithiums
Grignard
reagents
yield
various
enantioenriched
functionalized
tetraorganosilanes.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 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.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 28, 2025
Here,
we
report
the
Cu-catalyzed
asymmetric
carbene
insertion
into
both
Ge-H
and
Si-H
bonds
with
α-trifluoromethyl
diazo
compounds,
enabled
by
a
class
of
newly
developed
C2-symmetrical
bisoxazoline
ligands.
This
protocol
provides
an
efficient
method
for
preparation
enantioenriched
ogranogermanes
organosilanes,
featuring
broad
substrate
scope,
mild
reaction
conditions,
excellent
enantioselectivity,
low
catalyst
loading.
The
key
to
tolerance
is
use
SPSiBox
ligands
bearing
flexible
tunable
chiral
pocket.
Preliminary
mechanistic
studies
computational
unveiled
origin
induction
ligands,
mechanism
insertion.
not
only
new
construction
trifluoromethyl-containing
molecules
but
also
opens
avenue
Si-
Ge-containing
functional
molecules.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(12), P. 2775 - 2783
Published: April 24, 2024
Abstract
Achieving
precise
control
over
regioselectivity
and
stereoselectivity
in
the
hydroelementation
of
terminal
allenes
presents
a
formidable
challenge.
Despite
existence
various
catalytic
methods
for
their
functionalization,
this
entire
class
reactions
remains
significantly
underdeveloped
demands
extensive
research.
Here,
we
report
method
using
inexpensive
PN
5
P
pincer
cobalt
complexes
built
on
triazine
backbone.
Depending
substituent
at
ring,
enables
selective
synthesis
E‐alkenylsilane
or
Z‐allylborane
derivatives.
In
presented
approach,
silanes
pinacoloboranes
play
dualistic
role
simultaneous
activator
substrate
excluding
need
addition
external
bases.
Finally,
application
potential
obtained
compounds
was
demonstrated
by
performing
further
functionalizations
compounds.
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.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(7), P. 5077 - 5087
Published: March 20, 2024
1,1-Disilanes
are
synthetically
versatile
building
blocks,
owing
to
their
low
toxicity,
high
stability,
and
unique
structures.
However,
the
practical
synthesis
of
1,1-disilanes
is
still
a
challenge.
Despite
available
Fe-,
Co-,
La-,
B-catalyzed
protocols,
use
highly
reactive
reductants,
such
as
EtMgBr,
NaBHEt3,
or
KHMDS,
inevitably
requires
air-
moisture-free
conditions.
Herein,
we
report
homogeneous
Ni-catalyzed
mono-
dihydrosilylation
aliphatic
terminal
alkynes
under
either
air
water
conditions
neat
conditions,
affording
β-(E)-vinylsilanes
in
yields
with
complete
regioselectivity
stereoselectivity.
Importantly,
our
method
gram-scalable
sole
example
alkynes.
We
demonstrated
introduction
different
silyl
groups
through
stepwise
addition
each
silane
source
reaction
vessel.
Furthermore,
intermediates
were
characterized
spectroscopic/spectrometric
tools,
density
functional
theory
calculations
performed
understand
mechanism
origins
for
1,1-disilanes.