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.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(10), С. 2285 - 2291
Опубликована: Март 6, 2024
Abstract
P‐stereogenic
benzo‐fused
heterocycles
is
a
privileged
skeleton
due
to
their
outstanding
catalytic
properties
and
bioactivities.
However,
enantioselective
synthesis
still
underdeveloped.
Here
we
demonstrate
the
use
of
easily
accessible
racemic
H−P(O)
compounds
as
starting
materials
commercial
chiral
N
1
,
2
‐dimethyl‐1,2‐diphenylethane‐1,2‐diamine
ligand
in
combination
with
Cu(I)
catalysts
enable
an
attractive
dynamic
kinetic
C(
sp
2)−P
cross‐coupling
reaction.
This
protocol
not
only
exhibits
broad
substrate
scope
but
also
provides
general
access
diverse
range
useful
five‐,
six‐,
seven‐
eight‐membered
O,
P‐
containing
good
high
yields
enantioselectivities.
JACS Au,
Год журнала:
2025,
Номер
5(2), С. 578 - 585
Опубликована: Янв. 21, 2025
A
general
method
for
the
catalytic
asymmetric
α-selenenylation
of
simple
carbonyl
compounds
is
lacking.
Herein,
a
copper(I)-catalyzed
enantioselective
2-acylimidazoles
with
electrophilic
selenosulfonates
uncovered.
The
reaction
enjoys
advantages
mild
conditions,
easy
protocol,
and
broad
substrate
scopes
on
both
selenosulfonates.
Mechanistic
studies
reveal
pincer
Cu(I)-(S,S)-Ph-BOPA
complex
as
active
catalyst.
Some
traditional
selenenylation
reagents,
such
PhSeCl,
PhSeSePh,
2-(phenylselanyl)isoindoline-1,3-dione
lead
to
inferior
results
in
terms
yield
enantioselectivity,
highlighting
superiority
Finally,
several
transformations
based
2-acylimidazole
group
selenoether
are
successfully
carried
out,
demonstrating
synthetic
utilities
present
methodology.
Chiral
phospholane
ligands
and
catalysts
have
been
widely
applied
in
asymmetric
catalysis
synthesis.
However,
the
construction
of
chiral
skeleton
remains
challenging
primarily
relies
on
use
auxiliaries
or
resolution.
In
this
work,
a
highly
enantioselective
diastereoselective
synthesis
P-stereogenic
oxides
has
achieved
through
cobalt-catalyzed
desymmetric
hydroalkylation
strategy.
This
method
enables
two
discrete
stereocenters
with
excellent
yields
enantiomeric
excesses.
ACS Catalysis,
Год журнала:
2023,
Номер
13(24), С. 16240 - 16248
Опубликована: Дек. 5, 2023
An
adaptable,
sulfur-accelerated
photoaerobic
selenium-π-acid
ternary
catalyst
system
for
the
enantioselective
allylic
redox
functionalization
of
simple,
nondirecting
alkenes
is
reported.
In
contrast
to
related
photoredox
catalytic
methods,
which
largely
depend
on
olefinic
substrates
with
heteroatomic
directing
groups
unfold
high
degrees
stereoinduction,
current
protocol
relies
chiral,
spirocyclic
selenium-π-acids
that
covalently
bind
alkene
moiety.
The
performance
this
method
demonstrated
in
asymmetric,
lactonization
and
cycloamination
enoic
acids
unsaturated
sulfonamides,
respectively,
leading
an
averaged
enantiomeric
ratio
(er)
92:8.
Notably,
provides
first
time
entryway
pharmaceutically
relevant
3-pyrroline
motifs,
was
used
as
a
platform
access
3,4-dihydroxyproline
derivative
only
seven
steps
92:8
er.
Although
methods
for
synthesizing
chiral
phosphorus
scaffolds
are
available,
the
potential
of
this
molecular
chirality
remains
largely
unexplored.
Herein,
we
present
a
remote
desymmetrization
prochiral
biaryl
phosphine
oxides
through
an
organocatalytic
asymmetric
arylation.
This
metal-free
approach
enables
efficient
synthesis
wide
range
densely
functionalized
P(V)-stereogenic
compounds
with
good
to
excellent
yields
and
satisfactory
enantioselectivities.
Mechanistic
studies
reveal
that
hydrogen
bonding
ion-pairing
interactions
crucial
achieving
precise
stereocontrol
in
transformation.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(41)
Опубликована: Июль 9, 2024
Abstract
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.
