Here,
we
demonstrate
the
development
and
synthetic
applications
of
a
novel
class
diphosphine
ligands
(SPSiP)
based
on
chiral
spirosilabiindane
diol
(SPSiOL).
Starting
from
SPSiOL,
biphosphine
could
be
readily
prepared
in
three
steps
with
high
efficiency.
This
features
rigid
configuration,
large
dihedral
angle,
P–M–P
long
P–P
distance,
which
might
possess
unique
catalytic
reactivities.
The
potentials
SPSiPs
asymmetric
catalysis
have
also
been
preliminary
disclosed
by
Rh-catalyzed
hydrogenation,
tandem
hydrosilylation,
Pd-catalyzed
allylic
alkylation.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(36)
Опубликована: Май 20, 2022
Abstract
Optically
active
organosilanes
have
been
demonstrated
to
be
versatile
chiral
reagents
in
synthetic
chemistry
since
the
early
seminal
contributions
by
Sommer
and
Corriu.
Among
these
silicon‐containing
architectures,
monohydrosilanes,
which
bear
a
Si−H
bond,
hold
unique
position
because
of
their
facile
transformations
through
stereospecific
Si–carbon
or
Si–heteroatom
bond‐formation
reactions.
In
addition,
those
compounds
also
leveraged
as
for
alcohol
resolution,
auxiliaries,
mechanistic
probes,
well
potential
optoelectronic
materials.
This
Minireview
comprehensively
summarizes
synthesis
applications
silicon‐stereogenic
particularly
advances
transition‐metal‐catalyzed
asymmetric
this
class
functional
molecules.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(11)
Опубликована: Янв. 18, 2023
Here,
we
report
the
first
example
of
Ni-catalyzed
asymmetric
hydrosilylation
1,1-disubstituted
allenes
with
high
level
regioselectivities
and
enantioselectivities.
The
key
to
achieve
this
stereoselective
reaction
was
development
SPSiOL-derived
bisphosphite
ligands
(SPSiPO).
This
protocol
features
broad
substrate
scope,
excellent
functional
group,
heterocycle
tolerance,
thus
provides
a
versatile
method
for
construction
enantioenriched
tertiary
allylsilanes
in
straightforward
atom-economic
manner.
DFT
calculations
were
performed
reveal
mechanism
origins
enantioselectivity.
Organic Letters,
Год журнала:
2023,
Номер
25(21), С. 3859 - 3863
Опубликована: Май 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,
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(7)
Опубликована: Янв. 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.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(20)
Опубликована: Фев. 27, 2024
The
construction
of
silicon-stereogenic
silanols
via
Pd-catalyzed
intermolecular
C-H
alkenylation
with
the
assistance
a
commercially
available
L-pyroglutamic
acid
has
been
realized
for
first
time.
Employing
oxime
ether
as
directing
group,
silanol
derivatives
could
be
readily
prepared
excellent
enantioselectivities,
featuring
broad
substrate
scope
and
good
functional
group
tolerance.
Moreover,
parallel
kinetic
resolution
unsymmetric
substrates
further
highlighted
generality
this
protocol.
Mechanistic
studies
indicate
that
stabilize
Pd
catalyst
provide
chiral
induction.
Preliminary
computational
unveil
origin
enantioselectivity
in
bond
activation
step.
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.
