Chemistry - A European Journal,
Год журнала:
2023,
Номер
30(2)
Опубликована: Окт. 20, 2023
Abstract
As
a
crucial
class
of
functional
molecules
in
organosilicon
chemistry,
silanols
are
found
valuable
applications
the
fields
modern
science
and
will
be
potentially
powerful
framework
for
biologically
active
compounds
or
materials.
It
has
witnessed
an
increasing
demand
non‐natural
organosilanols,
as
well
progress
synthesis
these
structural
features.
From
classic
preparative
methods
to
catalytic
selective
oxidation
hydrosilanes,
electrochemical
hydrolysis
then
construction
most
challenging
silicon‐stereogenic
silanols.
This
review
summarized
catalyzed
via
hydroxylation
hydrosilanes
last
decade,
with
particular
emphasis
on
latest
elegant
developments
desymmetrization
strategy
enantioselective
from
dihydrosilanes.
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.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(19)
Опубликована: Янв. 9, 2023
Silanols
are
valuable
and
important
compounds,
which
have
found
widespread
applications
in
the
field
of
materials
science,
synthetic
chemistry,
medicinal
chemistry.
Although
a
handful
approaches
been
developed
for
synthesis
various
silanols,
access
to
enantioenriched
silicon-stereogenic
silanols
remains
underdeveloped.
This
Concept
article
intends
summarize
highlight
recent
advances
construction
endeavors
encourage
further
research
this
area.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(21), С. 11727 - 11734
Опубликована: Май 19, 2023
Despite
growing
progress
in
the
construction
of
silazanes,
catalytic
asymmetric
synthesis
silicon-stereogenic
silazanes
is
significantly
less
explored
and
remains
a
considerable
challenge.
Herein,
we
report
highly
enantioselective
via
dehydrogenative
coupling
dihydrosilanes
with
anilines.
The
reaction
readily
produces
wide
range
chiral
bis-silazanes
excellent
yields
stereoselectivities
(up
to
99%
ee).
Further
utility
this
process
demonstrated
by
polycarbosilazanes
featuring
configurational
main
chain
chirality.
In
addition,
straightforward
transformation
enantioenriched
delivers
various
silane
compounds
stereospecific
fashion,
illustrating
their
potential
utilities
as
synthons
for
novel
silicon-containing
functional
molecules.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(36)
Опубликована: Июль 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,
Год журнала:
2024,
Номер
53(9), С. 4648 - 4673
Опубликована: Янв. 1, 2024
This
review
summarizes
the
developments
of
X-type
silyl
ligands
for
transition-metal
catalysis,
elucidating
unique
features
σ-donating
ability
and
trans
-influence
silyl–metal
catalysts.
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.
