Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(37)
Опубликована: Июнь 25, 2024
Abstract
Chiral
allylic
alcohols
are
highly
prized
in
synthetic
chemistry
due
to
their
versatile
reactivity
stemming
from
both
alkenyl
and
hydroxyl
functionalities.
While
the
Nozaki–Hiyama–Kishi
(NHK)
reaction
is
a
widely
used
method
for
synthesis
of
alcohols,
it
suffers
drawbacks
such
as
use
toxic
chromium
salts,
high
amounts
metal
reductants,
poor
enantiocontrol.
To
address
these
limitations,
we
present
novel
approach
involving
metallaphotoredox‐catalyzed
asymmetric
NHK
production
chiral
alcohols.
This
marries
(pseudo)halides
with
aldehydes,
leveraging
synergistic
blend
nickel
catalyst
photocatalyst.
innovative
technique
enables
oxidative
addition
insertion
just
using
nickel,
diverging
significantly
conventional
pathway
mediated
by
salts.
The
adoption
this
methodology
holds
immense
promise
crafting
spectrum
intricate
compounds,
particularly
those
significance
pharmaceuticals.
Detailed
experimental
investigations
have
shed
light
on
metallaphotoredox
process,
further
enhancing
our
understanding
enabling
advancements.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Авг. 19, 2023
The
precise
and
efficient
construction
of
axially
chiral
scaffolds,
particularly
toward
the
aryl-alkene
atropoisomers
with
impeccably
full
enantiocontrol
highly
structural
diversity,
remains
greatly
challenging.
Herein,
we
disclose
an
organocatalytic
asymmetric
nucleophilic
aromatic
substitution
(SNAr)
reaction
aldehyde-substituted
styrenes
involving
a
dynamic
kinetic
resolution
process
via
hemiacetal
intermediate,
offering
novel
facile
way
to
significant
axial
styrene
scaffolds.
Upon
treatment
aldehyde-containing
bearing
(o-hydroxyl)aryl
unit
commonly
available
fluoroarenes
in
presence
peptide-phosphonium
salts,
SNAr
exquisite
bridged
biaryl
lactol
intermediate
undergoes
smoothly
furnish
series
decorated
various
functionalities
bioactive
fragments
high
stereoselectivities
(up
>99%
ee)
complete
E/Z
selectivities.
These
resulting
motifs
are
important
building
blocks
for
preparation
diverse
functionalized
styrenes,
which
have
great
potential
as
privileged
ligands/catalysts
synthesis.
Organic Letters,
Год журнала:
2024,
Номер
26(18), С. 3867 - 3871
Опубликована: Май 1, 2024
Herein,
a
highly
regio-,
enantio-,
and
diastereoselective
nickel-catalyzed
desymmetric
hydrocyanation
of
biaryl
dienes
for
the
simultaneous
construction
axial
central
chiralities
is
presented,
which
offers
convenient
approach
to
variety
tirenes
containing
union
an
axially
chiral
centrally
α-chiral
nitrile
under
mild
conditions
using
commercially
available
catalyst.
The
synthetic
utility
highlighted
by
development
novel
phosphine
ligand
biphenyl-based
diene
their
potential
applications
in
field
asymmetric
catalytic
reactions.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Апрель 23, 2024
Catalytic
cascade
transformations
of
simple
starting
materials
into
highly
functionalized
molecules
bearing
a
stereochemically
defined
multisubstituted
alkene,
which
are
important
in
medicinal
chemistry,
natural
product
synthesis,
and
material
science,
high
demand
for
organic
synthesis.
The
development
multiple
reaction
pathways
accurately
controlled
by
catalysts
derived
from
different
ligands
is
critical
goal
the
field
catalysis.
Here
we
report
cobalt-catalyzed
strategy
direct
coupling
inexpensive
1,3-enynes
with
two
acrylates
to
construct
diversity
1,3-dienes
containing
trisubstituted
or
tetrasubstituted
olefin.
Such
reactions
can
proceed
through
three
initiated
oxidative
cyclization
achieve
bond
formation
chemo-,
regio-
stereoselectivity
precisely
ligands,
providing
platform
tandem
carbon-carbon
bond-forming
reactions.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(37)
Опубликована: Июнь 25, 2024
Abstract
Chiral
allylic
alcohols
are
highly
prized
in
synthetic
chemistry
due
to
their
versatile
reactivity
stemming
from
both
alkenyl
and
hydroxyl
functionalities.
While
the
Nozaki–Hiyama–Kishi
(NHK)
reaction
is
a
widely
used
method
for
synthesis
of
alcohols,
it
suffers
drawbacks
such
as
use
toxic
chromium
salts,
high
amounts
metal
reductants,
poor
enantiocontrol.
To
address
these
limitations,
we
present
novel
approach
involving
metallaphotoredox‐catalyzed
asymmetric
NHK
production
chiral
alcohols.
This
marries
(pseudo)halides
with
aldehydes,
leveraging
synergistic
blend
nickel
catalyst
photocatalyst.
innovative
technique
enables
oxidative
addition
insertion
just
using
nickel,
diverging
significantly
conventional
pathway
mediated
by
salts.
The
adoption
this
methodology
holds
immense
promise
crafting
spectrum
intricate
compounds,
particularly
those
significance
pharmaceuticals.
Detailed
experimental
investigations
have
shed
light
on
metallaphotoredox
process,
further
enhancing
our
understanding
enabling
advancements.
