Synthesis,
Год журнала:
2024,
Номер
56(13), С. 2031 - 2046
Опубликована: Май 14, 2024
Abstract
Palladium
nanoparticles
are
dispersed
and
stabilized
in
organically
modified
silicate
(Pd@MTES),
characterized
by
a
number
of
spectroscopic
techniques,
including
FTIR,
TEM,
SEM,
XPS.
The
catalytic
effect
this
material
toward
the
hydrosilylation
aldehydes
ketones
is
explored,
scope
reaction
investigated,
with
26
examples
provided.
This
proceeds
under
neat
conditions
via
heterogeneous
catalysis,
mechanistic
pathway
supported
DFT
calculations
proposed.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(18)
Опубликована: Фев. 21, 2024
A
broadly
improved
second
generation
catalytic
two-phase
strategy
for
the
enantioselective
synthesis
of
stereogenic
at
phosphorus
(V)
compounds
is
described.
This
protocol,
consisting
a
bifunctional
iminophosphorane
(BIMP)
catalyzed
nucleophilic
desymmetrization
prochiral,
bench
stable
P(V)
precursors
and
subsequent
enantiospecific
substitution
allows
divergent
access
to
wide
range
C-,
N-,
O-
S-
substituted
containing
from
handful
enantioenriched
intermediates.
new
ureidopeptide
BIMP
catalyst/thiaziolidinone
leaving
group
combination
allowed
far
wider
substrate
scope
increased
reaction
efficiency
practicality
over
previously
established
protocols.
The
resulting
intermediates
could
then
be
transformed
into
an
even
greater
distinct
classes
by
displacement
remaining
as
well
allowing
further
diversification
downstream.
Density
functional
theory
(DFT)
calculations
were
performed
pinpoint
origin
enantioselectivity
BIMP-catalyzed
desymmetrization,
rationalize
how
superior
catalyst/leaving
leads
generality
in
our
second-generation
system,
shed
light
onto
observed
stereochemical
retention
inversion
pathways
when
performing
late-stage
S
ACS Catalysis,
Год журнала:
2024,
Номер
14(8), С. 6009 - 6015
Опубликована: Апрель 5, 2024
Rhodium(III)-catalyzed
atroposelective
C–H
selenylation
of
1-aryl
isoquinolines
has
been
achieved.
The
direct
reaction
between
and
2-(phenylselanyl)isoindoline-1,3-dione
in
the
presence
chiral
SCpRh(III)
complex
afforded
a
series
axially
isoquinoline
selenides
up
to
95%
yield
96%
ee.
features
mild
conditions
broad
substrate
scope.
DFT
calculations
revealed
that
C–Se
bond
formation
step
proceeds
through
formal
SN2
pathway.
Advanced Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 14, 2025
Abstract
Designing
drugs
to
intelligently
respond
different
ratio
of
biological
electron
donors/receptors
in
cancer
cells
and
normal
is
a
promising
strategy
achieve
highly
effective
less
toxic
chemotherapy.
Herein
by
employing
metal
center
active
the
selenium‐containing
electrophilic
drug
Ru(phtpy‐NO
2
)(phenSe)Cl
(
RuSe
)
with
strongly
polarization
characteristics
are
synthesized
which
can
efficiently
shuttle
electrons
from
donors
convert
oxidative
stress.
The
rate
transfer
at
selenium
1.81
times
higher
cell
environments
compared
environments.
This
results
being
14.98
more
lethal
than
cells.
Experimental
demonstrate
that
transport
process
carried
out
via
radicals
intermediate
positively
correlated
properties
atoms.
transports
bioactive
generate
large
number
superoxide
anions
leading
DNA
damage
decrease
mitochondrial
membrane
potential
further
activates
p53
signaling
pathway
amplifies
cell‐killing
effect
after
transporting
electrons.
work
provides
new
avenue
for
design
efficient
chemotherapeutic
agents.
Green Chemistry,
Год журнала:
2024,
Номер
26(4), С. 1846 - 1875
Опубликована: Янв. 1, 2024
Organocatalytic
enantioselective
cross-dehydrogenative
coupling
reaction
provides
a
great
opportunity
for
the
synthesis
of
highly
enantioenriched
molecules.
In
this
review,
recent
progress
in
field
is
summarized.
ACS Catalysis,
Год журнала:
2023,
Номер
13(24), С. 16300 - 16306
Опубликована: Дек. 6, 2023
Thiourea-assisted
chiral
bicyclic
imidazole
organocatalysts
were
designed,
synthesized,
and
successfully
applied
in
the
asymmetric
acylative
desymmetrization
of
P-prochiral
bisphenols.
Under
mild
conditions,
P-stereogenic
products
obtained
high
yields
(up
to
99%
yield)
with
enantioselectivities
ee).
Most
importantly,
reaction
could
also
achieve
satisfactory
results
under
1
mol
%
catalyst
loadings.
Mechanistic
studies
showed
that
synergistic
effect
including
covalent
activation
acyl
group
by
nucleophilic
noncovalent
H-bonding
π-interaction
between
substrate
was
crucial
for
efficient
construction
P-stereocenters.
Organic Letters,
Год журнала:
2024,
Номер
26(28), С. 5934 - 5939
Опубликована: Июль 5, 2024
A
palladium-catalyzed
asymmetric
tandem
Heck
and
carbonylation
of
bisallyl-phosphine
oxides
has
been
developed.
This
desymmetrization
process
provided
an
efficient
route
to
the
simultaneous
synthesis
a
chiral
P-stereogenic
center
quaternary
carbon
stereocenter
in
good
yields
with
diastereo-
enantioselectivities.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(41)
Опубликована: Июль 9, 2024
In
this
work,
we
describe
an
efficient
and
modular
method
for
enantiodivergent
accessing
P(V)-stereogenic
molecules
by
utilizing
the
catalytic
atroposelective
Catellani-type
C-H
arylation/desymmetric
intramolecular
N-arylation
cascade
reaction.
The
enantioselectivity
of
protocol
was
proved
to
be
tuned
polarity
solvent,
thus
providing
a
wide
range
both
chiral
enantiomers
in
moderate
good
yields
with
excellent
enantiomeric
excesses.
Noteworthy
is
that
strategy
developed
herein
represents
unprecedented
example
solvent-dictated
inversion
compounds.
ACS Catalysis,
Год журнала:
2024,
Номер
14(17), С. 13055 - 13064
Опубликована: Авг. 15, 2024
Catalytic
asymmetric
hydrofunctionalization
of
π-bonds
has
been
extensively
studied,
but
the
alkynes
that
affords
atropoisometric
products
remains
heavily
underexplored.
We
herein
report
[Rh(COD)OAc]2/Mg(NTf2)2-catayzed
highly
atroposelective
hydroselenation
two
classes
1-alkynylindoles
using
selenophenols,
where
Mg(II)
salt
both
activates
Rh
catalyst
and
provides
a
key
NTf2
anion
essential
for
catalytic
activity
enantioselectivity,
affording
C–N
axially
chiral
trisubstituted
olefins
bear
relatively
low
racemization
barrier
(ΔG‡
∼
27
kcal/mol).
The
system
features
high
activity,
mild
reaction
conditions,
good
functional
group
tolerance,
regio-,
(E)-,
enantioselectivity.
selenoether
moiety
in
product
framework
can
be
readily
functionalized
to
give
synthetically
useful
products.
