ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(22), P. 17039 - 17045
Published: Nov. 4, 2024
Herein,
we
demonstrate
the
successful
application
of
reductive
[2
+
4]
annulation
in
atroposelective
de
novo
benzene
ring
formation.
This
nickel-catalyzed
reaction
between
β-substituted
α-naphthylalkynes
and
a
biselectrophile
C(sp2)–X
type
offers
an
efficient
convenient
method
to
prepare
highly
enantioenriched
C1-symmetric
axially
chiral
biaryls
containing
two
preinstalled
functionalities.
The
coupling
products
can
be
used
as
versatile
synthetic
intermediates
access
bidentate
ligands
or
bifunctional
organocatalysts,
their
utility
asymmetric
catalysis
is
also
showcased
this
context.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(7)
Published: Jan. 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.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 1147 - 1157
Published: Jan. 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.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(28), P. 18892 - 18898
Published: July 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
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(22)
Published: March 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,
Journal Year:
2024,
Volume and Issue:
63(36)
Published: June 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.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 15, 2025
In
this
context,
we
report
a
nickel-catalyzed
dynamic
kinetic
asymmetric
reductive
arylation
of
aldehydes
with
racemic
heterobiaryl
triflates,
offering
series
axially
chiral
heterobiaryls
bearing
centrally
secondary
alcohol
moiety
in
highly
diastereo-
and
enantioselective
manner.
The
simultaneous
control
both
axial
central
stereogenic
elements
the
products
lies
stereoselective
nucleophilic
addition
configurationally
labile
hetereobiaryl
nickel
complex
to
formyl
group
aldehydes.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Aug. 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.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Dec. 30, 2024
The
strain-release-driven
reactions
of
bicyclo[1.1.0]butanes
(BCBs)
have
received
significant
attention
from
chemists.
Notably,
1,2-migratory
enabled
by
BCB-derived
B-ate
complexes
effectively
complement
the
initiated
common
BCBs.
desired
products
are
particularly
valuable
for
late-stage
transformations
due
to
presence
C-B
bond.
However,
asymmetric
mediated
boronate
progressed
slowly.
In
this
study,
we
develop
an
synthesis
atropisomers
featuring
cis-cyclobutane
boronic
esters
facilitated
1,2-carbon
or
boron
migration
ring-strained
complexes,
achieving
high
enantioselectivity.
reaction
is
compatible
with
various
aryl,
alkenyl,
alkyl
and
B
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(22)
Published: March 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.
