Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(1)
Published: Nov. 8, 2023
The
carbon-to-silicon
switch
in
formation
of
bioactive
sila-heterocycles
with
a
silicon-stereogenic
center
has
garnered
significant
interest
drug
discovery.
However,
metal-catalyzed
synthesis
such
scaffolds
is
still
its
infancy.
Herein,
rhodium-catalyzed
enantioselective
formal
[4+1]
cyclization
benzyl
alcohols
and
benzaldimines
been
realized
by
difunctionalization
secondary
silane
reagent,
affording
chiral-at-silicon
cyclic
silyl
ethers
sila-isoindolines,
respectively.
Mechanistic
studies
reveal
dual
role
the
rhodium-hydride
catalyst.
coupling
system
proceeds
via
enantio-determining
dehydrogenative
OH
silylation
alcohol
or
hydrosilylation
imine
to
give
an
enantioenriched
ether
silazane
intermediate,
same
rhodium
catalyst
also
enables
subsequent
intramolecular
cyclative
C-H
directed
pendent
Si-H
group.
Experimental
DFT
have
conducted
explore
mechanism
bond
alcohol,
where
Si-O
reductive
elimination
from
Rh(III)
hydride
intermediate
established
as
enantiodetermining
step.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(16), P. 10079 - 10134
Published: Aug. 1, 2023
This
review
summarizes
the
advancements
in
rhodium-catalyzed
asymmetric
C–H
functionalization
reactions
during
last
two
decades.
Parallel
to
rapidly
developed
palladium
catalysis,
rhodium
catalysis
has
attracted
extensive
attention
because
of
its
unique
reactivity
and
selectivity
reactions.
In
recent
years,
Rh-catalyzed
have
been
significantly
many
respects,
including
catalyst
design,
reaction
development,
mechanistic
investigation,
application
synthesis
complex
functional
molecules.
presents
an
explicit
outline
catalysts
ligands,
mechanism,
scope
coupling
reagents,
applications.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(25), P. 13887 - 13891
Published: April 8, 2021
Abstract
A
Rh‐catalyzed
asymmetric
synthesis
of
silicon‐stereogenic
dihydrodibenzosilines
featuring
axially
chiral
6‐membered
bridged
biaryls
is
demonstrated.
In
the
presence
a
Rh
I
catalyst
with
diphosphine
ligand,
wide
range
containing
both
silicon‐central
and
axial
chiralities
are
conveniently
constructed
in
excellent
enantioselectivities
via
dehydrogenative
C(sp
3
)−H
silylation.
Absolute
configuration
analysis
by
single‐crystal
X‐ray
structures
revealed
novel
silicon
central‐to‐axial
chirality
relay
phenomenon,
which
we
believe
will
inspire
further
research
field
catalysis
chiroptical
materials.
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.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: Feb. 14, 2022
The
tremendous
success
of
stereogenic
carbon
compounds
has
never
ceased
to
inspire
researchers
explore
the
potentials
silicon
compounds.
Intermolecular
C-H
silylation
thus
represents
most
versatile
and
straightforward
strategy
construct
C-Si
bonds,
however,
its
enantioselective
variant
been
scarcely
reported
date.
Herein
we
report
a
protocol
that
allows
for
intermolecular
bond
silylation,
leading
construction
wide
array
acyclic
Si-H
under
simple
mild
reaction
conditions.
Key
is
(1)
substrate
design
prevents
self-reaction
prochiral
silane
(2)
employment
more
reactive
rhodium
hydride
([Rh]-H)
catalyst
as
opposed
commonly
used
chloride
([Rh]-Cl)
catalyst.
This
work
unveils
opportunities
in
converting
arenes
into
value-added
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(48)
Published: Oct. 7, 2022
Silaspiranes
have
attracted
particular
attention
due
to
their
chiral
spiro-silicon
center,
which
serves
as
an
ideal
carbon
isostere
and
can
endow
spiro-analogs
with
distinct
properties.
Distinct
from
previously
reported
cyclization
or
cycloaddition
strategies
form
5/5-silaspiranes,
we
report
herein
the
asymmetric
dual
ring
expansion
of
spirosilabicyclobutanes
alkynes
synthesize
axially
spirosilabicyclohexenes
bearing
a
novel
6/6-silaspirane
framework.
DFT
(density
functional
theory)
calculations
provide
deep
insight
into
origin
high
enantioselectivity
controlled
by
sterically
demanding
binaphthyl
phosphoramidite
ligand.
Preliminary
studies
chiroptical
properties
indicate
that
one
spirosilabicyclohexene
analogs
exhibit
fluorescence
emission,
Cotton
effects
CPL
(circularly
polarized
luminescence)
activity.
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(9), P. 5185 - 5196
Published: April 15, 2022
Silacycle
is
one
of
the
most
essential
core
frameworks
in
silicon-containing
functional
molecules.
However,
structural
diversity
silacycles
has
been
largely
limited
due
to
lack
general
synthetic
methods.
Here,
we
report
an
efficient
synthesis
exo-cyclic
enoate-substituted
silacyclohexenes
by
ring
expansion
silacyclobutanes
with
allenoates.
The
reaction
proceeds
two
regioselectivities
during
Si–C
bond
insertion.
In
presence
Pd/PR3
catalyst,
unsubstituted
allenoates
undergo
β,
γ-insertion
form
a
Si–Cβ
bond,
giving
2-(E)-enoate-substituted
silacyclohexenes.
this
pathway,
chiral
phosphoramidite
ligand
used
construct
stereogenic
silicon
center
enantioselectively.
second
PtCl2
α-substituted
γ,
β-insertion
Si–Cγ
leading
3-(E)-enoate-substituted
control
experiments
and
density
theory
calculations
have
performed
understand
regio-
stereochemical
outcome
both
Pd-
Pt-catalyzed
reactions.
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.