Here,
we
demonstrate
the
development
and
synthetic
applications
of
a
novel
class
diphosphine
ligands
(SPSiP)
based
on
chiral
spirosilabiindane
diol
(SPSiOL).
Starting
from
SPSiOL,
biphosphine
could
be
readily
prepared
in
three
steps
with
high
efficiency.
This
features
rigid
configuration,
large
dihedral
angle,
P–M–P
long
P–P
distance,
which
might
possess
unique
catalytic
reactivities.
The
potentials
SPSiPs
asymmetric
catalysis
have
also
been
preliminary
disclosed
by
Rh-catalyzed
hydrogenation,
tandem
hydrosilylation,
Pd-catalyzed
allylic
alkylation.
European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
2022(46)
Опубликована: Ноя. 16, 2022
Abstract
Spiro
derivatives
are
important
scaffolding
substances
found
in
many
natural
products
and
pharmaceuticals.
In
the
last
decade,
numerous
new
approaches
based
on
multicomponent
reactions
have
been
explored
for
selective
efficient
development
of
spiro
using
various
organocatalytic
transition
metal‐based
catalytic
systems.
This
Review
discusses
pioneering
advances
field
stereoselective
preparation
derivatives.
These
include
Michael
cascade
cyclization
reactions,
cycloadditions,
diastereoselective
miscellaneous
synthesis
spiro‐hetero/carbocycles.
Advances
decade
made
it
possible
to
synthesize
compounds
with
good
excellent
stereoselectivity
under
appropriate
reaction
conditions.
However,
achieving
high
regioselectivity
several
described
remains
a
challenge.
Organocatalysts
transition‐metal‐based
catalysts
play
crucial
role
this
milestone.
Proposed
mechanisms
supporting
evidence
highlighted
Review.
The
progress
is
immense.
expected
that
synthetic
methods
will
soon
be
developed
can
widely
used
spiro‐heterocycles/carbocycles.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июль 30, 2024
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.
A
new
class
of
chiral
spiro
monophosphinites,
based
on
a
unique
non-C2-symmetric
3-oxo-1,1'-spirobiindane
scaffold
featuring
large
dihedral
angle,
has
been
effectively
designed
and
synthesized.
From
readily
accessible
resources,
these
monophosphinites
were
synthesized
via
eight
steps
in
16-32%
yields.
Their
excellent
performance
the
rhodium-catalyzed
asymmetric
hydrogenation
β-dehydroamino
acid
esters
underscores
critical
impact
angle
enhancing
activity
enantioselectivity.
An
efficient
and
straightforward
cobalt-catalyzed
regioselective
intramolecular
hydrosilylation
of
olefins
has
been
developed.
Regioselectivity
is
controlled
by
the
choice
ligands
substrates,
which
operate
through
two
distinct
mechanisms.
This
method
successfully
applied
to
both
terminal
internal
alkenes
phenyl
alkyl
tethers
between
silane
alkene,
demonstrating
its
versatility
across
a
broad
range
substrates.
Chemical Science,
Год журнала:
2023,
Номер
14(17), С. 4641 - 4646
Опубликована: Янв. 1, 2023
Spirodiphosphines
have
been
successfully
applied
in
various
asymmetric
catalytic
transformations.
However,
controlling
the
coordinating
conformations
by
direct
displacement
of
spiro
atom
remains
elusive.
Herein,
we
report
application
Si-centered
spirodiphosphine
(Si-SDP)
ligands
enantioselective
hydrosilylation/cyclization
1,6-enynes.
The
Si-SDPs
showed
superior
reactivity
to
existing
C2-symmetric
diphosphines,
allowing
generation
a
range
chiral
pyrrolidines
with
high
yields
and
enantioselectivity
(up
96%
yield
92%
ee)
at
room
temperature
low
catalyst
loading.
mechanistic
observations
were
consistent
modified
Chalk-Harrod
mechanism,
was
further
leveraged
for
room-temperature
Rh-catalyzed
hydrosilylation
alkynes.
A
class
of
C2-symmetrical
bisoxazoline
ligands
with
a
flexible
chiral
pocket
has
been
developed,
which
could
be
readily
prepared
in
three
steps
from
enantiopure
SPSiOLs.
This
type
presented
high
level
enantioselectivity
for
the
Cu-catalyzed
asymmetric
carbene
insertion
Ge–H
bonds
α-trifluoromethyl
diazo
compounds,
thus
providing
an
efficient
method
preparation
enantioenriched
ogranogermanes.
reac-tion
features
broad
substrates
scope,
mild
reaction
conditions,
excellent
enantioselectivity,
and
low
catalyst
loading.
Preliminary
mechanistic
studies
un-veiled
that
this
might
undergo
concerted
mechanism,
computational
unveiled
origin
induction
SPSiBox
ligand.
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.
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:
2022,
Номер
134(36)
Опубликована: Май 20, 2022
Abstract
Optically
active
organosilanes
have
been
demonstrated
to
be
versatile
chiral
reagents
in
synthetic
chemistry
since
the
early
seminal
contributions
by
Sommer
and
Corriu.
Among
these
silicon‐containing
architectures,
monohydrosilanes,
which
bear
a
Si−H
bond,
hold
unique
position
because
of
their
facile
transformations
through
stereospecific
Si–carbon
or
Si–heteroatom
bond‐formation
reactions.
In
addition,
those
compounds
also
leveraged
as
for
alcohol
resolution,
auxiliaries,
mechanistic
probes,
well
potential
optoelectronic
materials.
This
Minireview
comprehensively
summarizes
synthesis
applications
silicon‐stereogenic
particularly
advances
transition‐metal‐catalyzed
asymmetric
this
class
functional
molecules.
Angewandte Chemie,
Год журнала:
2023,
Номер
135(11)
Опубликована: Янв. 18, 2023
Abstract
Here,
we
report
the
first
example
of
Ni‐catalyzed
asymmetric
hydrosilylation
1,1‐disubstituted
allenes
with
high
level
regioselectivities
and
enantioselectivities.
The
key
to
achieve
this
stereoselective
reaction
was
development
SPSiOL‐derived
bisphosphite
ligands
(SPSiPO).
This
protocol
features
broad
substrate
scope,
excellent
functional
group,
heterocycle
tolerance,
thus
provides
a
versatile
method
for
construction
enantioenriched
tertiary
allylsilanes
in
straightforward
atom‐economic
manner.
DFT
calculations
were
performed
reveal
mechanism
origins
enantioselectivity.
