Organometallics,
Год журнала:
2024,
Номер
44(1), С. 3 - 7
Опубликована: Дек. 16, 2024
A
series
of
chiral
pincer
iridium
complexes
supported
by
oxazoline-containing
PCCN-type
ligands
were
synthesized.
Among
them,
the
(tBuPCCNtBu)IrHCl
complex
bearing
sterically
bulky
tBu
groups
both
at
P
atom
and
on
oxazoline
ring
exhibits
high
efficiency
enantioselectivity
for
asymmetric
dual
dehydrogenative
silylation
C(sp3)–H
bonds.
This
reaction
provides
an
enantioselective
approach
to
oxa-spirosilanes
with
a
stereogenic
silicon
center
from
readily
available
diarylsilanes.
Organic Letters,
Год журнала:
2024,
Номер
26(14), С. 2811 - 2816
Опубликована: Янв. 16, 2024
Herein
we
have
developed
a
highly
practical
and
efficient
one-step
coupling
protocol
for
the
synthesis
of
chiral
spiro
diphosphine
ligands,
especially
oxa-spiro
ligands
O-SDP,
which
showed
excellent
reactivity
diastereoselectivity
in
asymmetric
hydrogenation
key
intermediate
Sacubitril.
It
should
be
noted
that
could
operated
on
kilogram
scale,
resulting
ruthenium
catalyst
O-SDP
hydrogenate
Sacubitril
an
industrial
scale.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(70)
Опубликована: Сен. 23, 2023
Abstract
Silaspiranes
bearing
a
spiro‐silicon
center
are
promising
ring
frameworks
for
the
synthesis
of
novel
spirocyclic
molecules
possessing
unique
properties.
Development
efficient
methods
towards
these
structures
has
therefore
attracted
considerable
attentions
synthetic
chemists.
This
minireview
highlights
representative
advances
in
field,
and
is
categorized
into
four
parts
according
to
formation
strategies:
cyclization,
annulation,
expansion
cycloaddition.
Organic Letters,
Год журнала:
2023,
Номер
25(43), С. 7810 - 7815
Опубликована: Окт. 26, 2023
A
rhodium-catalyzed
enantioselective
hydroboration/cyclization
reaction
of
1,6-enynes
is
achieved
by
employing
a
spirosiladiphosphine
ligand.
The
process
allows
the
synthesis
five-membered
hetero-
and
carbocycles
bearing
boron
handle
with
high
levels
activity
selectivity.
Various
enynes
organoboranes
(HBdan,
HBpin,
HBmp,
HBamm)
have
been
accommodated,
containing
terminal
alkynes
integrated
into
for
first
time.
yields
selectivities
transformation
highlight
synthetic
utility
these
novel
ligands.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(7)
Опубликована: Янв. 8, 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.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(12), С. 9027 - 9030
Опубликована: Май 30, 2024
A
Lewis
acid-catalyzed
intramolecular
Hosomi–Sakurai
reaction
of
o-(allylsilyl)benzaldehyde/ketone
has
been
developed.
The
proceeds
through
simultaneous
C–Si
bond
cleavage
and
C–C
reconstruction.
This
protocol
provides
a
rapid
approach
for
the
synthesis
allyl-substituted
benzoxasiloles
under
mild
conditions.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(42)
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.
Organic Letters,
Год журнала:
2024,
Номер
26(35), С. 7436 - 7441
Опубликована: Авг. 26, 2024
Here,
we
report
the
development
and
application
of
a
novel
class
spirosilacycle-based
diphosphine
ligands
(SPOSiPs).
This
type
ligand
could
be
readily
prepared
in
two
steps
with
high
efficiency
starting
from
enantiopure
spirobiphenoxasilin-diol
(SPOSiOL).
According
to
structural
analysis
SPOSiP
its
PdCl2
complex,
SPOSiPs
possess
flexible
chiral
pocket
feature
rigid
configuration,
large
dihedral
angle,
long
P–P
distance,
P–M–P
bite
angle
their
metal
complexes.
The
potentials
asymmetric
catalysis
have
also
been
preliminarily
disclosed.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Ноя. 15, 2024
Carbon-silicon-switch
strategy,
replacing
one
specific
carbon
atom
in
organic
molecules
with
a
silicon,
has
garnered
significant
interest
for
developing
new
functional
molecules.
However,
the
influence
of
reaction
regarding
its
selectivity
and
reactivity
by
carbon-silicon-switch
strategy
far
less
been
investigated.
Here
we
discover
an
unusual
effect
enantioselective
construction
silicon-stereogenic
center.
It
is
found
that
there
change
desymmetrization
silacyclohexadienones
using
asymmetric
conjugate
addition
or
oxidative
Heck
aryl/alkyl
nucleophiles
when
compared
their
analogues
cyclohexadienones.
Specifically,
leads
to
reversal
enantioselectivity
arylzinc
as
nucleophile
same
chiral
catalyst,
results
totally
different
arylboronic
acid
nucleophile.
Control
experiments
density
theory
(DFT)
calculations
have
shown
comes
from
unique
stereoelectronic
feature
silicon.
Silicon
incorporated
into
place
under
principle
that,
given
they
belong
periodic
group,
could
be
similar.
Here,
authors
perform
desymmetrizations
on
silacyclohexenone
analogue,
two
substrates
yielding
opposite
enantiomers,
showing
our
understanding
similarities
atoms
incomplete.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(36)
Опубликована: Июнь 19, 2024
Abstract
Functionalization
of
Si
‐bound
methyl
group
provides
an
efficient
access
to
diverse
organosilanes.
However,
the
asymmetric
construction
silicon‐stereogenic
architectures
by
functionalization
has
not
yet
been
described
despite
recent
significant
progress
in
producing
chiral
silicon.
Herein,
we
disclosed
enantioselective
silylmethyl
involving
aryl
alkyl
1,5‐palladium
migration
naphthalenes
possessing
enantioenriched
stereogenic
silicon
center,
which
are
inaccessible
before.
It
is
worthy
note
that
realization
induction
at
step
metal
itself
remains
challenging.
Our
study
constitutes
first
reaction.
The
key
success
discovery
and
fine‐tuning
different
substituents
α,α,α,α‐tetraaryl‐1,3‐dioxolane‐4,5‐dimethanol
(TADDOL)‐based
phosphoramidites,
ensure
enantioselectivity
desired
reactivity.
