Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 14, 2025
A
diverse
range
of
Pd(II)-catalyzed
enantioselective
C-H
activation
reactions
have
been
developed
to
construct
point,
axial,
and
planar
chirality.
Despite
the
importance
chiral
biaryl
scaffolds
in
bioactive
molecules
ligands,
atroposelective
functionalization
at
meta-position
remains
a
significant
challenge.
Here,
we
realized
rare
remote
meta-C-H
with
monoprotected
amino
acid
(MPAA)
ligand
racemic
transient
norbornene
mediator.
The
reaction
starts
ortho-C-H
via
kinetic
resolution
give
biaryl-palladium
intermediate,
which
subsequently
undergoes
Catellani
relay
afford
meta-functionalized
products
(S-factors
up
458).
obtained
enantioenriched
quinoline-based
atropisomers
are
ubiquitous
natural
products,
pharmaceuticals,
functional
materials.
Moreover,
unprecedented
meta-alkenylation
alkynylation
also
using
this
approach.
wide
synthetic
applications
8-aryl
quinolines,
including
synthesis
novel
P,N-ligand
materials
CPL
activity,
demonstrated.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(28)
Опубликована: Май 2, 2022
Abstract
Among
sulfoximine
derivatives
containing
a
chiral
sulfur
center,
benzothiadiazine‐1‐oxides
are
important
for
applications
in
medicinal
chemistry.
Here,
we
report
that
the
combination
of
an
achiral
cobalt(III)
catalyst
and
pseudo‐
C
2
‐symmetric
H
8
‐binaphthyl
carboxylic
acid
enables
asymmetric
synthesis
from
sulfoximines
dioxazolones
via
enantioselective
C−H
bond
cleavage.
With
optimized
protocol,
with
several
functional
groups
can
be
accessed
high
enantioselectivity.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Авг. 29, 2023
The
N-N
atropisomer,
as
an
important
and
intriguing
chiral
system,
was
widely
present
in
natural
products,
pharmaceutical
lead
compounds,
advanced
material
skeletons.
anisotropic
structural
characteristics
caused
by
its
special
axial
rotation
have
always
been
one
of
the
challenges
that
chemists
strive
to
overcome.
Herein,
we
report
efficient
method
for
enantioselective
synthesis
axially
frameworks
via
a
cobalt-catalyzed
atroposelective
C-H
activation/annulation
process.
reaction
proceeds
under
mild
conditions
using
Co(OAc)2·4H2O
catalyst
with
salicyl-oxazoline
(Salox)
ligand
O2
oxidant,
affording
variety
products
high
yields
enantioselectivities.
This
protocol
provides
approach
facile
construction
atropisomers
further
expands
range
derivatives.
Additionally,
electrocatalysis,
desired
were
also
successfully
achieved
good
excellent
efficiencies
ACS Catalysis,
Год журнала:
2023,
Номер
13(7), С. 4250 - 4260
Опубликована: Март 13, 2023
Herein,
we
disclose
an
efficient
cobalt-catalyzed
enantioselective
C–H
activation
and
annulation
of
benzamides
with
alkenes.
This
transformation
is
facilitated
via
the
commercially
available
cobalt(II)
catalyst
in
presence
easily
prepared
chiral
salicyl-oxazoline
(Salox)
ligand,
which
provides
facile
access
to
(R)
or
(S)
enantiomers
dihydroisoquinolone
derivatives.
It
noticeable
that
reaction
proceeded
efficiently
within
extremely
short
time
from
10
30
min
under
mild
conditions.
A
broad
range
alkenes
bear
various
functional
substituents
have
been
shown
good
compatibility
deliver
targeted
products
high
yields
enantioselectivities
(51
examples,
up
98%
yield
99%
ee).
The
gram
scale
experiment
removal
directing
group
further
demonstrate
practicability
this
protocol
potential
industrial
applications.
Density
theory
calculations
elucidate
mechanism,
spin-state
change
olefin
insertion
step
accelerates
subsequent
C–N
reductive
elimination,
identified
as
stereo-determining
step.
AIM
analysis
indicates
π
interactions
are
vital
for
controlling
switching
stereoselectivity.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(2), С. 1209 - 1223
Опубликована: Янв. 3, 2024
Owing
to
its
diverse
activation
processes
including
single-electron
transfer
(SET)
and
hydrogen-atom
(HAT),
visible-light
photocatalysis
has
emerged
as
a
sustainable
efficient
platform
for
organic
synthesis.
These
provide
powerful
avenue
the
direct
functionalization
of
C(sp3)–H
bonds
under
mild
conditions.
Over
past
decade,
there
have
been
remarkable
advances
in
enantioselective
bond
via
combined
with
conventional
asymmetric
catalysis.
Herein,
we
summarize
involving
discuss
two
main
pathways
this
emerging
field:
(a)
SET-driven
carbocation
intermediates
are
followed
by
stereospecific
nucleophile
attacks;
(b)
photodriven
alkyl
radical
further
enantioselectively
captured
(i)
chiral
π-SOMOphile
reagents,
(ii)
stereoselective
transition-metal
complexes,
(iii)
another
distinct
stereoscopic
species.
We
aim
key
reaction
design,
catalyst
development,
mechanistic
understanding,
new
insights
into
rapidly
evolving
area
research.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 14, 2025
A
diverse
range
of
Pd(II)-catalyzed
enantioselective
C-H
activation
reactions
have
been
developed
to
construct
point,
axial,
and
planar
chirality.
Despite
the
importance
chiral
biaryl
scaffolds
in
bioactive
molecules
ligands,
atroposelective
functionalization
at
meta-position
remains
a
significant
challenge.
Here,
we
realized
rare
remote
meta-C-H
with
monoprotected
amino
acid
(MPAA)
ligand
racemic
transient
norbornene
mediator.
The
reaction
starts
ortho-C-H
via
kinetic
resolution
give
biaryl-palladium
intermediate,
which
subsequently
undergoes
Catellani
relay
afford
meta-functionalized
products
(S-factors
up
458).
obtained
enantioenriched
quinoline-based
atropisomers
are
ubiquitous
natural
products,
pharmaceuticals,
functional
materials.
Moreover,
unprecedented
meta-alkenylation
alkynylation
also
using
this
approach.
wide
synthetic
applications
8-aryl
quinolines,
including
synthesis
novel
P,N-ligand
materials
CPL
activity,
demonstrated.
