Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: July 11, 2024
A
strong
and
confined
Brønsted
acid
catalyzed
enantioselective
cyclization
of
bis(methallyl)silanes
provides
enantioenriched
Si-stereogenic
silacycles.
High
enantioselectivities
up
to
96.5:3.5
er
were
obtained
for
a
range
bis(methallyl)silanes.
NMR
ESI-MS
studies
reveal
that
the
formation
covalent
adduct
irreversibly
inhibits
turnover.
Remarkably,
we
found
acetic
as
an
additive
promotes
collapse
this
adduct,
enabling
full
Experimental
investigation
density
functional
theory
(DFT)
calculations
conducted
elucidate
origin
phenomenon
observed
enantioselectivity.
Synthesis,
Journal Year:
2022,
Volume and Issue:
54(08), P. 1939 - 1950
Published: Jan. 3, 2022
Abstract
In
recent
years,
transition-metal-catalyzed
enantioselective
C–H
bond
functionalization
has
emerged
as
a
powerful
and
attractive
synthetic
approach
to
access
silicon-stereogenic
centers,
which
provides
impetus
for
the
innovation
of
chiral
organosilicon
chemistry.
This
short
review
summarizes
advances
in
construction
silanes
via
functionalization.
We
endeavor
highlight
great
potential
this
methodology
hope
that
will
shed
light
on
new
perspectives
inspire
further
research
emerging
area.
1
Introduction
2
Enantioselective
Functionalization
Induced
by
Oxidative
Addition
an
Aryl-OTf
Bond
3
Silacyclobutane
4
Directing-Group-Assisted
5
Dehydrogenative
C–H/Si–H
Coupling
5.1
C(sp2)–H
Silylation
5.2
C(sp3)–H
6
Summary
Outlook
European Journal of Organic Chemistry,
Journal Year:
2021,
Volume and Issue:
2021(44), P. 6006 - 6014
Published: Sept. 21, 2021
Abstract
The
asymmetric
synthesis
of
Si‐stereogenic
silanes
has
attracted
great
attention
due
to
the
increasing
values
Si‐containing
functional
molecules
in
synthetic
chemistry,
medicinal
and
material
chemistry.
Merging
organosilicon
chemistry
with
transition‐metal‐catalyzed
C−H
approach
led
rich
sets
new
reactions
holding
values.
This
Minireview
aims
summarize
advances
construction
through
activation
approach.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(31)
Published: May 26, 2022
Despite
growing
progress
in
the
construction
of
chiral
organosilicon
compounds,
catalytic
asymmetric
synthesis
silicon-stereogenic
silanols
is
less
explored
and
remains
a
considerable
challenge.
Herein,
we
report
first
enantioselective
by
hydrolytic
oxidation
dihydrosilanes.
This
practical
procedure
features
ambient
reaction
conditions,
high
atom
economy,
good
functional-group
compatibility,
H2
as
only
by-product,
produces
wide
range
valuable
bis-silanols
decent
yields
with
excellent
chemo-
stereoselectivity.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(14), P. 8476 - 8483
Published: July 1, 2022
Despite
the
growing
demand
for
enantioenriched
silicon-stereogenic
silanols
in
materials
science,
medicinal
chemistry,
and
modern
synthetic
catalytic
asymmetric
synthesis
of
which
remains
a
considerable
challenge
compared
with
their
carbinol
analogues.
Herein,
copper-catalyzed
desymmetrization
silanediols
various
functionalized
chiral
is
demonstrated.
The
reaction
features
high
atom
economy,
decent
yield
excellent
stereoselectivity,
H2
as
sole
byproduct.
Key
to
success
discrimination
gem-diol
groups
silanediol
relies
on
an
enantioselective
σ-bond
metathesis
process.
Further
straightforward
elaboration
delivers
several
interesting
silane
scaffolds
without
loss
enantiopurities.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(51)
Published: Nov. 4, 2022
Abstract
Strategies
on
the
construction
of
enantiomerically
pure
silicon‐stereogenic
silanes
generally
relies
desymmetrization
prochiral
and
symmetric
substrates.
However,
dynamic
kinetic
asymmetric
transformations
organosilicon
compounds
have
remained
underdeveloped
unforeseen
owing
to
a
lack
an
effective
method
for
deracemization
static
silicon
stereocenters.
Here
we
report
first
Rh‐catalyzed
intramolecular
hydrosilylation
(DyKAH)
with
“silicon‐centered”
racemic
hydrosilanes
that
enables
facile
preparation
benzosiloles
in
good
yields
excellent
enantioselectivities.
The
special
rhodium
catalyst
controlled
by
non‐diastereopure‐type
mixed
phosphine‐phosphoramidite
ligand
axial
chirality
multiple
stereocenters
can
induce
enantioselectivity
efficiently
this
novel
DyKAH
reaction.
Density
functional
theory
(DFT)
calculations
suggest
amide
moiety
chiral
plays
important
role
facilitating
S
N
2
substitution
chloride
ion
realize
inversion
center.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(9)
Published: Jan. 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,
Journal Year:
2023,
Volume and Issue:
29(19)
Published: Jan. 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.
