Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 2, 2024
Abstract
The
efficient
construction
of
chalcogen‐atom‐based
chiral
compounds
remains
a
challenge,
despite
the
importance
organoselenium
and
organosulfur
in
life
materials
science.
Chalcogen
atoms
can
form
net
attractive
interactions
called
chalcogen
bonds,
but
it
is
an
undeveloped
tool
to
assist
asymmetric
catalysis.
Herein,
we
report
enantioselective
insertion
platform
install
stereogenic
center
bearing
selenyl
thiocyano
functional
groups.
Our
method
operates
by
synergistic
catalysis
guanidine
achiral
dirhodium
complex
three‐component
or
four‐component
reaction,
through
Se−S
bond
into
carbene
species,
competing
successfully
with
spontaneous
racemic
process
showing
high
regioselectivity.
As
elucidated
spectroscopic
experiments
computational
studies,
unique
mechanism
involving
as
well
hydrogen
bonding
was
established
account
for
enantiocontrol.
stereoselectivity
holds
broad
array
selenylthiocyanatopropanoates,
which
showed
excellent
anti‐inflammatory
toward
IL‐1β
low
cytotoxicity.
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.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Март 3, 2025
A
highly
enantioselective
electrophilic
selenylation/semipinacol
rearrangement
of
allenols
has
been
developed,
which
is
enabled
by
the
cooperative
catalysis
a
chiral
sulfide
and
an
achiral
sulfonic
acid.
The
designed
synthesized
catalyst
selenylating
reagent
play
crucial
role
in
enhancing
both
enantioselectivity
reactivity.
This
approach
exhibits
excellent
regio-,
chemo-,
enantioselectivity,
providing
access
to
diverse
enantioenriched
cyclopentanones
featuring
arylselenovinyl-substituted
quaternary
carbon
stereocenter.
Furthermore,
these
products
can
be
transformed
into
synthetically
valuable
alkyne,
vinyl
bromide,
aniline
derivatives.
Mechanistic
studies
reveal
that
combination
acid
not
only
facilitates
formation
catalytically
active
species,
but
also
governs
reaction.
Meanwhile,
density
functional
theory
calculations
disclose
four
hydrogen
bond
interactions
π‧‧‧π
interaction
are
responsible
for
observed
enantioselectivity.
Rearrangement
reactions
serve
as
steps
syntheses
biologically
provide
intellectual
conceptual
curiosities
within
broad
field
organic
chemistry.
Here,
authors
report
allenols,
catalysed
Lewis
base.
A
novel
P(═O)R2-directed
asymmetric
catalytic
olefination
has
been
developed,
enabling
efficient
access
to
carbon–nitrogen
axially
chiral
products
with
excellent
yields
(up
92%)
and
enantioselectivity
99%
enantiomeric
excess).
The
synergistic
coordination
of
phosphine
oxide
functionality
l-pGlu-OH
the
Pd
metal
center,
serving
as
an
directing
group
ligand,
was
key
success
this
C–H
functionalization
system.
reaction
demonstrated
a
broad
substrate
scope,
yielding
33
distinct
C–N
axial
products.
absolute
configuration
unambiguously
confirmed
via
X-ray
diffraction
analysis.
Additionally,
three
representative
applications
were
showcased,
involving
reduction
oxidation
produce
phosphines
related
derivatives.
plausible
cycle
mechanism
proposed,
supported
by
detailed
experimental
studies.
Aggregates
in
system
identified
aggregation-induced
polarization
experiments.
Developing
platinum
group
metal
(PGM)-free
electrodes
with
high
efficiency
and
stability
is
the
ultimate
goal
for
cost-effective
anion
exchange
membrane
water
electrolysis
(AEMWE),
while
it
poses
a
significant
challenge
to
PGM-free
catalysts.
Here,
we
present
reconstructed
NiMoSex
(r-NiMoSex)
nanorods
as
highly
efficient
catalysts
oxygen
evolution
reaction
(OER),
in
which
Se
can
induce
fast
structural
reconstruction,
thereby
creating
flexible
surface.
This
approach
constructs
successive
ion
channels
mass
transfer,
thus
significantly
facilitating
OER
performance.
Consequently,
r-NiMoSex-based
AEMWE
enables
an
exceptional
current
density
of
3
A
cm–2
at
2.05
V,
be
stably
run
1
1.70
V
190
h
low
attenuation
rate
48.1
μV
h–1,
surpassing
most
previously
reported
More
importantly,
r-NiMoSex
maintain
stable
performance
after
almost
half-year
placement.
strategy
contributes
developing
next-generation
durable
green
hydrogen
production.
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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 2, 2024
The
efficient
construction
of
chalcogen-atom-based
chiral
compounds
remains
a
challenge,
despite
the
importance
organoselenium
and
organosulfur
in
life
materials
science.
Chalcogen
atoms
can
form
net
attractive
interactions
called
chalcogen
bonds,
but
it
is
an
undeveloped
tool
to
assist
asymmetric
catalysis.
Herein,
we
report
enantioselective
insertion
platform
install
stereogenic
center
bearing
selenyl
thiocyano
functional
groups.
Our
method
operates
by
synergistic
catalysis
guanidine
achiral
dirhodium
complex
three-component
or
four-component
reaction,
through
Se-S
bond
into
carbene
species,
competing
successfully
with
spontaneous
racemic
process
showing
high
regioselectivity.
As
elucidated
spectroscopic
experiments
computational
studies,
unique
mechanism
involving
as
well
hydrogen
bonding
was
established
account
for
enantiocontrol.
stereoselectivity
holds
broad
array
selenylthiocyanatopropanoates,
which
showed
excellent
anti-inflammatory
toward
IL-1β
low
cytotoxicity.
Chemical Communications,
Год журнала:
2024,
Номер
60(53), С. 6753 - 6756
Опубликована: Янв. 1, 2024
An
efficient
Rh(III)-catalyzed
enantioselective
C-H
alkynylation
of
isoquinolines
is
disclosed.
The
1-aryl
with
hypervalent
iodine-alkyne
reagents
proceeded
in
DMA
at
room
temperature
the
presence
2.5
mol%
chiral
SCpRh(III)
complex
along
20
AgSbF
