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.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(3)
Опубликована: Ноя. 2, 2023
With
the
rapid
development
of
asymmetric
catalysis,
demand
for
enantioselective
synthesis
complex
and
diverse
molecules
with
different
chiral
elements
is
increasing.
Owing
to
unique
features
atropisomerism,
catalytic
atropisomers
has
attracted
a
considerable
interest
from
chemical
science
community.
In
particular,
introducing
additional
elements,
such
as
carbon
centered
chirality,
heteroatomic
planar
helical
into
provides
an
opportunity
incorporate
new
properties
axially
compounds,
thus
expanding
potential
applications
atropisomers.
Thus,
it
important
perform
transformations
synthesize
bearing
multiple
elements.
spite
challenges
in
transformations,
recent
years,
chemists
have
devised
powerful
strategies
under
organocatalysis
or
metal
synthesizing
wide
range
enantioenriched
Therefore,
become
emerging
field.
This
review
summarizes
progress
this
field
indicates
challenges,
thereby
promoting
horizon.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(7)
Опубликована: Янв. 2, 2024
Chromium-catalyzed
enantioselective
Nozaki-Hiyama-Kishi
(NHK)
reaction
represents
one
of
the
most
powerful
approaches
for
formation
chiral
carbon-heteroatom
bond.
However,
construction
sterically
encumbered
tetrasubstituted
stereocenter
through
NHK
still
posts
a
significant
challenge.
Herein,
we
disclose
cobalt-catalyzed
aza-NHK
ketimine
with
alkenyl
halide
to
provide
convenient
synthetic
approach
manufacture
enantioenriched
α-vinylic
amino
acid.
This
protocol
exhibits
excellent
functional
group
tolerance
99
%
ee
in
cases.
Additionally,
this
asymmetric
reductive
method
is
also
applicable
aldimine
access
trisubstituted
stereogenic
centers.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(15), С. 10857 - 10867
Опубликована: Апрель 8, 2024
The
asymmetric
cross-coupling
of
unsaturated
bonds,
hampered
by
their
comparable
polarity
and
reactivity,
as
well
the
scarcity
efficient
catalytic
systems
capable
diastereo-
enantiocontrol,
presents
a
significant
hurdle
in
organic
synthesis.
In
this
study,
we
introduce
highly
adaptable
photochemical
cobalt
catalysis
framework
that
facilitates
chemo-
stereoselective
reductive
cross-couplings
between
common
aldehydes
with
broad
array
carbonyl
iminyl
compounds,
including
N-acylhydrazones,
aryl
ketones,
aldehydes,
α-keto
esters.
Our
methodology
hinges
on
synergistic
mechanism
driven
photoredox-induced
single-electron
reduction
subsequent
radical–radical
coupling,
all
precisely
guided
chiral
catalyst.
Various
optically
enriched
β-amino
alcohols
unsymmetrical
1,2-diol
derivatives
(80
examples)
have
been
synthesized
good
yields
(up
to
90%
yield)
high
stereoselectivities
>20:1
dr,
99%
ee).
Of
particular
note,
approach
accomplishes
unattainable
transformations
disparate
partners
without
reliance
any
external
photosensitizer,
thereby
further
emphasizing
its
versatility
cost-efficiency.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(28), С. 18892 - 18898
Опубликована: Июль 5, 2024
Herein,
we
designed
a
reaction
for
the
desymmetrization-addition
of
cyclopropenes
to
imines
by
leveraging
synergy
between
photoredox
and
asymmetric
cobalt
catalysis.
This
protocol
facilitated
synthesis
series
chiral
functionalized
cyclopropanes
with
high
yield,
enantioselectivity,
diastereoselectivity
(44
examples,
up
93%
yield
>99%
ee).
A
possible
mechanism
involving
cyclopropene
desymmetrization
Co-H
species
imine
addition
Co-alkyl
was
proposed.
study
provides
novel
route
important
extends
frontier
metallaphotoredox
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 1147 - 1157
Опубликована: Янв. 3, 2025
This
study
describes
a
photoredox/cobalt
dual-catalyzed
asymmetric
Grignard-type
addition
reaction,
enabling
the
synthesis
of
axially
chiral
hexatomic
(six–six)
N-heterobiaryls
bearing
extra
secondary
alcohol
unit
via
an
efficient
dynamic
kinetic
transformation
racemic
N-heterobiaryl
triflate
substrates.
The
conversion
facilitated
both
photoredox
and
classical
reductive
reaction
conditions
exhibits
good
functional
group
tolerance,
broad
substrate
scope,
satisfactory
stereoselectivity.
Furthermore,
control
experiments
density
theory
calculations
provide
preliminary
mechanistic
insights.
Green Chemistry,
Год журнала:
2023,
Номер
25(21), С. 8459 - 8493
Опубликована: Янв. 1, 2023
This
review
comprehensively
summarizes
visible
light-induced
difunctionalization
strategies
for
alkene
and
alkyne
systems
in
metal-free
conditions
with
literature
coverage
up
to
July
2023.
Chemical Science,
Год журнала:
2024,
Номер
15(12), С. 4564 - 4570
Опубликована: Янв. 1, 2024
We
present
NHC-catalyzed
atroposelective
esterification
of
prochiral
dialdehydes,
delivering
enantioenriched
axially
chiral
diaryl
ethers.
Matched
kinetic
resolutions
amplify
the
enantioselectivity
by
removing
minor
enantiomers
via
over-functionalization.
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 4638 - 4647
Опубликована: Март 12, 2024
Axially
chiral
diaryl
ethers
make
up
a
unique
class
of
atropisomers
bearing
restricted
rotation
about
the
C–O
bond.
Methods
for
expedient
synthesis
axially
ether-based
structures
have
been
largely
underdeveloped.
Herein,
we
developed
an
efficient
metal-catalyzed
desymmetrization
strategy
to
unveil
formation
and
centrally
dual
in
high
diastereo-
enantioselectivity.
The
protocol
leverages
cobalt-catalyzed
photoreductive
enantioselective
couplings
dialdehyde
alkyne
deliver
stereogenicity,
ether
scaffold
is
equipped
with
useful
synthetic
handles
including
formyl,
hydroxyl,
allyl
groups,
as
has
demonstrated
carboxylic
acid
potential
ligand
asymmetric
catalysis.
