Abstract
With
the
aim
to
explore
metal‐ligand
cooperation
across
Pd−S
linkages,
we
designed
a
quinoline‐based
PNS
tridentate
ligand
and
prepared
Pd(II)
complexes
thereof.
Optimal
solubility
stability
of
dicationic
complex
[(PNS)Pd(II)]
2
2+
IV
were
achieved
with
B(C
6
F
5
)
4
–
as
counter‐anion.
It
adopts
thiolate‐bridged
dimeric
structure
(PdS)
core,
but
readily
activates
hydrosilanes
linkage.
The
resulting
mononuclear
hydride
[(PNS
SiR3
)Pd(II)H]
+
VI
was
characterized
by
multi‐nuclear
NMR
spectroscopy
Si−H
bond
coordination/activation
studied
computationally.
Complex
found
efficiently
catalyze
hydrosilylation
alkynes,
internal
well
terminal,
good
stereo
regioselectivity.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(29), С. 20092 - 20106
Опубликована: Июль 15, 2024
Developing
a
general
method
that
leads
to
the
formation
of
different
classes
chiral
bioactive
compounds
and
their
stereoisomers
is
an
attractive
but
challenging
research
topic
in
organic
synthesis.
Furthermore,
despite
great
value
asymmetric
transfer
hydrogenation
(ATH)
both
synthesis
pharmaceutical
industry,
monohydrogenation
unsymmetrical
1,2-diketones
remains
underdeveloped.
Here,
we
report
aryloxy
group-assisted
highly
regio-,
diastereo-,
enantioselective
ATH
racemic
1,2-diketones.
The
work
produces
myriad
enantioenriched
dihydroxy
ketones,
further
transformations
furnish
all
eight
diaryl
triols,
polyphenol,
emblirol,
glycerol-type
natural
products.
Mechanistic
studies
calculations
reveal
two
working
modes
group
switching
regioselectivity
from
more
reactive
carbonyl
less
one,
potential
on
solving
synthetic
issues
has
been
clearly
demonstrated.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 27, 2024
Asymmetric
transfer
hydrogenation
(ATH)
has
been
recognized
as
a
highly
valuable
strategy
that
allows
access
to
enantioenriched
substances
and
widely
applied
in
the
industrial
production
of
drug
molecules.
However,
despite
great
success
ATH
ketones,
efficient,
regio-
stereoselective
on
enones
remains
underdeveloped.
Moreover,
optically
pure
acyloins
1,2-diols
are
both
extremely
useful
building
blocks
organic
synthesis,
medicinal
chemistry,
materials
science,
but
concise
asymmetric
approaches
allowing
different
types
have
scarcely
discovered.
We
report
this
paper
first
efficient
readily
accessible
β,γ-unsaturated
α-diketones.
The
protocol
affords
four
fashion.
synthetic
value
work
showcased
by
divergent
synthesis
related
natural
products.
systematic
mechanistic
studies
density
functional
theory
(DFT)
calculations
illustrated
origin
reactivity
divergence,
revealed
roles
aromatic
aliphatic
substituents
substrates,
provided
range
unique
rationales
not
disclosed
ATH-related
studies.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Pyridine
is
a
versatile
structural
unit
found
in
broad
spectrum
of
pharmaceuticals,
agrochemicals,
and
materials.
Achieving
selective
meta-functionalization
under
mild
conditions
remains
challenging
due
to
its
inherent
electronic
properties.
In
this
work,
we
accomplished
photoinduced
method
for
meta-selective
sulfonylation
pyridines,
facilitated
by
an
electron
donor-acceptor
(EDA)
complex
between
iodide
ions
sulfonyl
chlorides.
The
reaction
proceeds
via
oxazino-pyridine
intermediate,
with
chloride
acting
as
the
radical
precursor.
This
protocol
stands
out
mild,
photocatalyst-free
conditions,
high
C5-selectivity,
good
scalability,
offering
promising
approach
synthesis
meta-sulfonylated
pyridines.
Chemical Communications,
Год журнала:
2024,
Номер
60(53), С. 6745 - 6748
Опубликована: Янв. 1, 2024
The
cooperation
between
a
geometrically
constrained,
highly
electrophilic
phosphorus(V)
center,
and
an
electronically
rich
tetradentate
bis(amidophenolate)
ligand
enables
the
cleavage
of
CO
bond
from
typical
aldehydes
ketones
delivering
iminio
phosphoramidate
species.
amphiphilic
nature
these
products,
which
is
demonstrated
through
their
reaction
with
Lewis
acids
bases,
use
as
mild
source
silylium
cations
silanes,
allowing
selective
reductive
coupling
to
ethers
under
catalytic
conditions.
Molecules,
Год журнала:
2024,
Номер
29(16), С. 3743 - 3743
Опубликована: Авг. 7, 2024
The
development
of
new
chiral
ligands
with
simple
and
modular
structure
represents
a
challenging
direction
in
the
design
efficient
homogeneous
transition
metal
catalysts.
Herein,
we
report
on
asymmetric
hydrogenation
prochiral
ketones
catalyzed
by
iridium
complexes
alkane-diyl-based
P,N,O-type
highly
structure.
role
(i)
P-N
N-O
backbone
potentially
tridentate
ligands,
(ii)
number,
position
relative
configuration
their
stereogenic
elements
(iii)
effect
NH
OH
subunits
activity
enantioselectivity
catalytic
reactions
are
studied.
systematic
variation
ligand
comparative
experiments
shed
light
different
mechanistic
aspects
iridium-catalyzed
reaction.
catalysts
containing
central
chirality
provided
high
enantioselectivities
(up
to
98%
Organometallics,
Год журнала:
2024,
Номер
43(22), С. 2972 - 2980
Опубликована: Ноя. 13, 2024
Phosphine
ligands
bearing
amidine
groups
were
designed
for
the
synthesis
of
complexes
in
which
a
metal
center
and
cooperate.
Several
palladium
amidinate
synthesized
from
these
ligands.
The
reaction
with
various
organic
molecules
containing
an
acidic
OH
group
gave
complexes.
In
reaction,
O–H
bond
was
activated
by
metal–ligand
cooperation
(MLC).
