Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(27)
Опубликована: Апрель 23, 2024
There
is
a
pressing
need
for
methods
that
can
connect
enantioenriched
organic
compounds
with
readily
accessible
building
blocks
via
asymmetric
functionalization
of
unreactive
chemical
bonds
in
synthesis
and
medicinal
chemistry.
Herein,
the
chemoselective
cleavage
two
unactivated
C(Ar)-O
same
molecule
disclosed
first
time
through
an
unusual
nickel-catalyzed
carbomagnesiation.
This
reaction
facilitates
evolution
novel
atroposelective
ring-opening
difunctionalization.
Utilizing
available
dibenzo
bicyclic
substrates,
diverse
valuable
axially
chiral
biaryls
are
furnished
high
efficiencies.
Synthetic
elaborations
showcase
application
potential
this
method.
The
features
method
include
good
atom-economy,
multiple
roles
nucleophile,
simple
catalytic
system
enables
precise
magnesiation
α-C(Ar)-O
bond
arylation
β-C(Ar)-O
bond.
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(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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(22)
Опубликована: Март 26, 2024
Abstract
Upgrading
CO
2
to
value‐added
chiral
molecules
via
catalytic
asymmetric
C−C
bond
formation
is
a
highly
important
yet
challenging
task.
Although
great
progress
on
the
of
centrally
carboxylic
acids
has
been
achieved,
construction
axially
with
never
reported
date.
Herein,
we
report
first
synthesis
,
which
enabled
by
nickel‐catalyzed
dynamic
kinetic
reductive
carboxylation
racemic
aza‐biaryl
triflates.
A
variety
acids,
are
valuable
but
difficult
obtain
catalysis,
generated
in
an
enantioconvergent
version.
This
new
methodology
features
good
functional
group
tolerance,
easy
scale‐up,
facile
transformation
and
avoids
cumbersome
steps,
handling
organometallic
reagents
using
stoichiometric
materials.
Mechanistic
investigations
indicate
process
induced
nickel
catalysis.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июнь 15, 2024
Axially
chiral
biaryl
δ-amino
acids
possess
significantly
different
conformational
properties
and
environment
from
centrally
amino
acids,
therefore,
have
drawn
considerable
attention
in
the
fields
of
synthetic
medicinal
chemistry.
Herein,
a
novel
phenanthroline-potassium
catalyst
has
been
developed
by
constructing
well-organized
axially
ligand
composed
one
1,10-phenanthroline
unit
two
1,1'-bi-2-naphthol
(BINOL)
units.
In
presence
this
catalyst,
good
to
excellent
yields
enantioselectivities
(up
99
%
yield,
98
:
2
er)
achieved
ring-opening
alcoholytic
dynamic
kinetic
resolution
variety
lactams,
thereby
providing
an
efficient
protocol
for
catalytic
asymmetric
synthesis
unnatural
acid
derivatives.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 23, 2024
Atropisomeric
biaryls
bearing
carbonyl
groups
have
attracted
increasing
attention
due
to
their
prevalence
in
diverse
bioactive
molecules
and
crucial
role
as
efficient
organo-catalysts
or
ligands
asymmetric
transformations.
However,
preparation
often
involves
tedious
multiple
steps,
the
direct
synthesis
via
carbonylation
has
scarcely
been
investigated.
Herein,
we
report
an
palladium-catalyzed
enantioconvergent
aminocarbonylation
of
racemic
heterobiaryl
triflates
with
amines
dynamic
kinetic
transformation
(DyKAT).
This
protocol
features
a
broad
substrate
scope
excellent
compatibility
for
rapid
construction
axially
chiral
amides
good
high
yields
enantioselectivities.
Detailed
mechanistic
investigations
discover
that
base
can
impede
intramolecular
hydrogen
bond-assisted
axis
rotation
products,
thus
allowing
success
achieve
enantioselectivity.
Moreover,
achieved
be
directly
utilized
N,N,N-pincer
copper-catalyzed
enantioselective
formation
C(sp3)-N
C(sp3)-P
bonds.
Axially
containing
not
only
exist
various
drug
candidates
but
also
serve
authors
transformation.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(22)
Опубликована: Март 26, 2024
Abstract
Upgrading
CO
2
to
value‐added
chiral
molecules
via
catalytic
asymmetric
C−C
bond
formation
is
a
highly
important
yet
challenging
task.
Although
great
progress
on
the
of
centrally
carboxylic
acids
has
been
achieved,
construction
axially
with
never
reported
date.
Herein,
we
report
first
synthesis
,
which
enabled
by
nickel‐catalyzed
dynamic
kinetic
reductive
carboxylation
racemic
aza‐biaryl
triflates.
A
variety
acids,
are
valuable
but
difficult
obtain
catalysis,
generated
in
an
enantioconvergent
version.
This
new
methodology
features
good
functional
group
tolerance,
easy
scale‐up,
facile
transformation
and
avoids
cumbersome
steps,
handling
organometallic
reagents
using
stoichiometric
materials.
Mechanistic
investigations
indicate
process
induced
nickel
catalysis.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(29), С. 20477 - 20493
Опубликована: Июль 10, 2024
Cobalt
complexes
with
chiral
quinox
ligands
effectively
promote
the
enantioselective
conjugate
addition
of
enones
using
aryl,
heteroaryl,
and
alkenyl
halides
sulfonates.
Additionally,
a
cobalt
complex
strongly
donating
diphosphine,
BenzP*,
successfully
catalyzes
asymmetric
reductive
arylation
alkenylation
α,β-unsaturated
amides.
Both
catalytic
systems
show
broad
scopes
tolerance
sensitive
functional
groups.
reactions
can
be
scaled
up
low
loadings
catalysts.
Experimental
results
density
theory
(DFT)
calculations
suggest
new
mechanism
elementary
1,4-addition
aryl
cobalt(I)
complexes.
