Science,
Journal Year:
2024,
Volume and Issue:
384(6697), P. 793 - 798
Published: May 16, 2024
Stereoselective
construction
of
γ-
and
δ-stereocenters
in
carbonyl
compounds
is
a
pivotal
objective
asymmetric
synthesis.
Here,
we
report
chiral
bifunctional
oxazoline-pyridone
ligands
that
enable
enantioselective
palladium-catalyzed
remote
γ-C−H
(hetero)arylations
free
cycloalkane
carboxylic
acids,
which
are
essential
carbocyclic
building
blocks
organic
The
reaction
establishes
γ-tertiary
α-quaternary
stereocenters
simultaneously
up
to
>99%
enantiomeric
excess,
providing
access
wide
range
cyclic
synthons
bioactive
molecules.
sequential
editing
two
methylene
C–H
bonds
can
be
achieved
by
using
with
opposite
configuration
construct
carbocycles
containing
three
centers.
Enantioselective
δ-C−H
(hetero)arylation
also
realized
establish
particularly
challenging
classical
methodologies.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(48), P. 25948 - 25953
Published: Nov. 20, 2023
Selective
oxidation
of
the
γ-C–H
bonds
from
abundant
amine
feedstocks
via
palladium
catalysis
is
a
valuable
transformation
in
synthesis
and
medicinal
chemistry.
Despite
advances
on
this
topic
past
decade,
there
remain
two
significant
limitations:
C–H
activation
aliphatic
amines
requires
an
exogenous
directing
group
except
for
sterically
hindered
α-tertiary
amines,
practical
catalytic
system
C(sp3)–H
hydroxylation
using
green
oxidant,
such
as
oxygen
or
aqueous
hydrogen
peroxide,
has
not
been
developed
to
date.
Herein,
we
report
ligand-enabled
selective
γ-C(sp3)–H
sustainable
peroxide
(7.5–10%,
w/w).
Enabled
by
CarboxPyridone
ligand,
series
primary
(1°),
piperidines,
morpholines
(2°)
were
hydroxylated
at
γ-position
with
excellent
monoselectivity.
This
method
provides
avenue
wide
range
including
γ-amino
alcohols,
β-amino
acids,
azetidines.
The
retention
chirality
reaction
allows
rapid
access
chiral
starting
pool.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(9), P. 6535 - 6546
Published: April 15, 2024
Palladium-catalyzed
C–H
annulation
reactions
represent
a
compelling
strategy
to
construct
complex
ring
systems
with
high
step
economy.
While
there
are
many
approaches
annulate
structures
by
activation
of
single
bond,
transformations
that
proceed
multiple
bonds
less
explored.
This
is
especially
true
for
examples
where
one
the
reacting
located
at
an
sp3
center.
However,
exciting
developments
in
palladium-catalyzed
continue
expand
scope
these
and
provide
innovative
strategies
challenging
carbon–carbon
bonds.
From
discoveries,
sequential
activations
have
emerged
as
powerful
tool
access
through
C(sp2)–H/C(sp3)–H
or
C(sp3)–H/C(sp3)–H
In
this
Perspective,
we
showcase
recent
use
order
highlight
synthetic
potential
activation-enabled
annulations
inspire
future
disconnections
diverse
scaffold
synthesis.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: March 28, 2025
Heteroatom-doped
polyaromatic
hydrocarbons
show
great
potential
for
advancing
photoelectric
materials.
SVI=N
doping,
characterized
by
soft-hard
atom
binding,
donor-acceptor
transmission,
and
chiroptical
tuning,
provides
a
powerful
approach
further
optimizing
the
performance
functionality
of
these
However,
introduction
chiral
sulfur(VI)
has
been
formidable
challenge
due
to
intricate
enantioselective
discrimination
embedded
linkages
with
heteroatoms
in
systems.
Herein,
we
establish
an
Pd-catalyzed
desymmetrization
diaryl
sulfoximines
sulfondiimines
access
SVI=N-doped
heterocycles
high
yields
enantioselectivities.
The
flexibility
rigidity
molecule
distinct
effect
on
enantioselectivity.
split
aromatic
compounds
exhibit
C-H···π
interactions
involving
additive
TMCPA
ligand
S-aryl
motif,
producing
(R)-configuration,
while
combined
opposite
(S)-configuration
restricted
bond
rotation.
photophysical
study
demonstrates
carbazole-based
heterocycle
intense
double
absorption
peaks
favorable
luminescence
dissymmetry
factor.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(23)
Published: Feb. 7, 2024
Abstract
The
advancement
of
sustainable
chemistry
and
changes
in
the
economy
are
strongly
intertwined.
Reaction
time,
cost
savings,
moderate
temperatures,
generation
fewest
byproducts
frequently
achieved
by
using
catalytic
processes.
Herein,
we
report
C−H
olefination
imidazo[1,2a]
pyridine
carboxamides
with
various
acrylates
presence
Pd
(OAc)
2
O
as
oxidant
aqueous
ethanol
rather
than
non‐ecofriendly
solvents.
activation
features
most
user‐friendly
reaction
conditions,
excellent
yield
well
plenty
substrate
scope
applicable
for
deuteriation
corresponding
heteroarenes
D
O.
Experimental
mechanistic
studies
indicate
that
step
succeeded
after
formation
tetra
coordinated
square
planer
Pd‐substrate
adduct.
