Chinese Journal of Organic Chemistry,
Год журнала:
2023,
Номер
43(10), С. 3352 - 3352
Опубликована: Янв. 1, 2023
Owing
to
its
unique
structure
and
properties,
silicon-stereogenic
silanes
have
displayed
valuable
application
prospects
in
the
fields
of
organic
synthesis,
functional
materials
biomedicine,
received
extensive
attention
from
chemists.In
recent
years,
methods
for
construction
center
been
rapidly
developed,
especially
use
transition
metal
catalysis
conduct
desymmetrization
prochiral
silanes.Among
them,
asymmetric
catalytic
Si-H/X-H
dehydrogenative
coupling
(Si-CADC)
using
dihydrosilane
as
substrate
has
become
an
important
approach
key
technology
center,
because
advantages
high
efficiency,
atomic
economy,
good
structural
diversity
enantioselectivity.According
different
reaction
categorie
products,
this
review
will
mainly
summarize
discuss
three
stages:
(1)
tandem
strategy
construct
tetrasubstituted
silanes,
(2)
intramolecular
Si-H/C-H
cyclic
monohydrosilanes,
(3)
intermolecular
a
variety
ayclic
silanes.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(9)
Опубликована: Янв. 10, 2023
We
report
the
first
highly
enantioselective
construction
of
silicon-stereocenters
by
asymmetric
enamine
catalysis.
An
unprecedented
desymmetric
intramolecular
aldolization
prochiral
siladials
was
thus
developed
for
facile
access
multifunctional
silicon-stereogenic
silacycles
in
high
to
excellent
enantioselectivity.
With
an
enal
moiety,
these
adducts
could
be
readily
elaborated
diverse
synthesis
compounds,
and
late-stage
modification.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(9), С. 4994 - 5000
Опубликована: Фев. 24, 2023
Chiral
organosilanes
do
not
exist
in
nature
and
are
therefore
absent
from
the
"chiral
pool".
As
a
consequence,
synthetic
approaches
toward
enantiopure
silanes,
stereogenic
at
silicon,
rather
limited.
While
catalytic
asymmetric
desymmetrization
reactions
of
symmetric
organosilicon
compounds
have
been
developed,
utilization
racemic
silanes
dynamic
kinetic
transformation
(DYKAT)
or
resolution
(DKR)
would
significantly
expand
breadth
accessible
Si-stereogenic
compounds.
We
now
report
DYKAT
allyl
enabled
by
strong
confined
imidodiphosphorimidate
(IDPi)
catalysts,
providing
access
to
silyl
ethers.
The
products
this
reaction
easily
converted
into
useful
monohydrosilanes.
propose
spectroscopically
experimentally
supported
mechanism
involving
epimerization
catalyst-bound
intermediate.
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(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.
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
This
study
demonstrates
the
rhodium-catalyzed
divergent
synthesis
of
5-,
5,6-,
and
8-membered
silacyclic
compounds,
such
as
benzosilole,
silolosiline,
disilocine,
from
(2-hydrosilylaryl)acetylenes.
To
achieve
high
product
selectivity,
intra-
intermolecular
reactions
are
controlled
by
tuning
mono-
bidentate
phosphine
ligands
on
rhodium
catalyst
precursor.
Deuterium
labeling
experiments
computational
studies
reveal
that
annulation
reaction
proceeds
via
hydride
transfer
to
alkyne
moiety.
