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.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(12), С. 6944 - 6952
Опубликована: Март 15, 2023
Enantioselective
metallaphotoredox
catalysis,
which
combines
photoredox
catalysis
and
asymmetric
transition-metal
has
become
an
effective
approach
to
achieve
stereoconvergence
under
mild
conditions.
Although
many
impressive
synthetic
approaches
have
been
developed
access
central
chirality,
the
construction
of
axial
chirality
by
still
remains
underexplored.
Herein,
we
report
two
visible
light-induced
cobalt-catalyzed
reductive
couplings
biaryl
dialdehydes
synthesize
axially
chiral
aldehydes
(60
examples,
up
98%
yield,
>19:1
dr,
>99%
ee).
This
protocol
shows
good
functional
group
tolerance,
broad
substrate
scope,
excellent
diastereo-
enantioselectivity.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(25), С. 11364 - 11376
Опубликована: Июнь 10, 2022
Pd-catalyzed
sequential
hydroamination
of
readily
available
1,3-enynes
is
reported.
The
redox-neutral
process
provides
an
efficient
route
to
synthesize
a
broad
scope
imidazolidinones,
thiadiazolidines,
and
imidazolidines.
Asymmetric
generates
series
synthetically
valuable,
enantioenriched
imidazolidinones.
Mechanistic
studies
revealed
that
the
transformation
occurred
via
intermolecular
enyne
pathway
give
allene
intermediate.
Subsequent
intramolecular
intermediate
proceeded
under
Curtin-Hammett
principle
provide
imidazolidinone
products.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(30)
Опубликована: Май 24, 2022
Abstract
One
of
the
most
straightforward
approaches
to
access
chiral
silanes
is
catalytic
enantioselective
hydrosilylation.
Although
significant
advances
have
been
achieved
in
construction
either
a
carbon‐stereogenic
center
or
silicon‐stereogenic
through
hydrosilylation,
simultaneous
establishment
carbon‐
and
an
acyclic
molecule
single
intermolecular
hydrosilylation
remained
undeveloped.
Herein,
unprecedented
cobalt‐catalyzed
regio‐,
diastereo‐
1,3‐dienes
presented,
enabling
transformation.
A
wide
range
bearing
were
generated
high
efficiency
stereoselectivity.
Functionalization
enantioenriched
delivered
variety
valuable
building
blocks
that
are
otherwise
difficult
access.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(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 International Edition,
Год журнала:
2022,
Номер
61(51)
Опубликована: Ноя. 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.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(6), С. 3588 - 3598
Опубликована: Фев. 3, 2023
Catalytic
enantioselective
functionalization
of
cyclobutenes
constitutes
a
general
and
modular
strategy
for
construction
enantioenriched
complex
cyclobutanes
bearing
multiple
stereogenic
centers,
as
chiral
four-membered
rings
are
common
motifs
in
biologically
active
molecules
versatile
intermediates
organic
synthesis.
However,
synthesis
through
such
remained
significantly
limited.
Herein,
we
report
series
unprecedented
cobalt-catalyzed
carbon-carbon
bond
forming
reactions
that
initiated
carbometalation.
The
protocols
feature
diastereo-
introduction
allyl,
alkynyl,
functionalized
alkyl
groups.
Mechanistic
studies
indicated
an
unusual
1,3-cobalt
migration
subsequent
β-carbon
elimination
cascade
process
occurred
the
allyl
addition.
These
new
discoveries
established
elementary
cobalt
catalysis
extension
diversity
nucleophiles
transformations
cyclobutenes.
