Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(13)
Опубликована: Янв. 14, 2022
We
report
herein
an
unprecedented
gold
and
oxidative
NHC
relay
catalysis
that
enables
highly
enantioselective
cascade
annulation
between
readily
available
α-amino-ynones
with
enals.
This
method
utilizes
the
in
situ-generated
pyrrolin-4-ones
as
a
novel
versatile
synthon,
which
engage
α,β-unsaturated
acylazolium
intermediates
generated
from
enals
by
to
produce
pyrrole-fused
lactones
high
yield
excellent
enantioselectivity.
Synthetic
utility
of
lactone
products
is
also
demonstrated
facile
conversion
densely
functionalized
pyrroles
yields
stereopurity.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(18), С. 10422 - 10450
Опубликована: Янв. 1, 2021
This
review
highlights
a
decade-long
journey
of
Au-catalyzed
1,2-difunctionalization
reactions
C–C
multiple
bonds
that
have
been
realized
due
to
the
productive
integration
Au(
i
)/Au(
iii
)catalysis
with
unique
π-activation
mode
gold
complexes.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(16), С. 7089 - 7095
Опубликована: Апрель 18, 2022
Presented
herein
is
the
first
report
of
enantioselective
Au(I)/Au(III)
redox
catalysis,
enabled
by
a
newly
designed
hemilabile
chiral
(P,N)-ligand
(ChetPhos).
The
potential
this
concept
has
been
demonstrated
development
1,2-oxyarylation
and
1,2-aminoarylation
alkenes
which
provided
direct
access
to
medicinally
relevant
3-oxy-
3-aminochromans
(up
88%
yield
99%
ee).
DFT
studies
were
carried
out
unravel
enantiodetermining
step,
revealed
that
stronger
trans
influence
phosphorus
allows
selective
positioning
substrate
in
C2-symmetric
environment
present
around
nitrogen,
imparting
high
level
enantioselectivity.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(16), С. 8810 - 8816
Опубликована: Апрель 16, 2023
Herein,
we
report
a
gold-catalyzed
Heck
reaction
facilitated
by
the
ligand-enabled
Au(I)/Au(III)
redox
catalysis.
The
elementary
organometallic
steps
such
as
migratory
insertion
and
β-hydride
elimination
have
been
realized
in
catalytic
fashion
for
first
time
gold
chemistry.
present
methodology
not
only
overcomes
limitations
of
previously
known
transition
metal-catalyzed
reactions
requirement
specialized
substrates
formation
mixture
regioisomeric
products
result
undesirable
chain-walking
process
but
also
offers
complementary
regioselectivity
compared
to
other
metal
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(6), С. 3660 - 3674
Опубликована: Фев. 5, 2024
Ligand-enabled
oxidative
addition
of
Csp2-X
bonds
to
Au(I)
centers
has
recently
appeared
as
a
valuable
strategy
for
the
development
catalytic
RedOx
processes.
Several
cross-coupling
reactions
that
were
previously
considered
difficult
achieve
reported
lately,
thus
expanding
synthetic
potential
gold(I)
complexes
beyond
traditional
nucleophilic
functionalization
π-systems.
MeDalPhos
played
an
important
role
in
this
and,
despite
several
studies
on
alternative
structures,
remains,
so
far,
only
general
ligand
such
process.
We
report
herein
discovery
and
DFT-enabled
structural
optimization
new
family
hemilabile
(P∧N)
ligands
can
promote
aryl
iodides
gold(I).
These
flexible
ligands,
which
possess
common
2-methylamino
heteroaromatic
N-donor
motif,
are
structurally
electronically
tunable,
being
easily
accessible
affordable.
The
corresponding
shown
outperform
reactivity
(MeDalPhos)Au(I)
series
alkoxy-
amidoarylations
alkenes.
Their
comparatively
higher
further
highlighted
thiotosylation
iodides,
challenging
unreported
C–S
reaction
could
not
be
achieved
under
classical
Pd(0/II)
catalysis
allows
divergent
access
sulfur
derivatives.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 7, 2025
Recently,
ligand-promoted
Au(I)/Au(III)-catalyzed
cross-coupling
reactions
with
aryl
iodides
have
garnered
considerable
attention.
Here,
we
report
the
first
visible-light-driven
gold-catalyzed
cross-couplings
of
challenging
bromides.
In
presence
a
(P,
N)-gold(I)
catalyst
and
an
acridinium
photocatalyst
under
blue
LED
irradiation,
C-O
coupling
bromides
carboxylic
acids
was
achieved,
soon
it
found
that
this
photoinduced
appliable
for
other
C-C,
C-N,
C-S
bond
formation.
Experimental
computational
studies
suggest
involves
two
discrete
energy
transfer
(EnT)
events:
first,
from
photosensitizer
produces
excited-state
gold(I)
complex
allows
bottleneck
oxidative
addition
to
form
Au(III)
second,
reductive
elimination
aryl-Au(III)
regenerate
Au(I).
Collectively,
new
synergistic
catalytic
method
developed
here
highlights
tremendous
potential
photochemical
gold
catalysis
via
organogold
complexes,
as
well
its
facilitate
drug
discovery
due
biocompatibility
mildness
reaction
conditions.
The
rapid
recombination
of
electron-hole
pairs
and
limited
substrates
are
the
most
critical
factors
astricting
effect
catalytic
therapy.
Thus,
two-dimensional
interplanar
heterojunction
(BiOCl/Bi2O3)
that
prolongs
lifetime
excited
electrons
holes
extends
selectivity
under
ultrasound
irradiation
is
prepared
to
facilitate
high-performance
cancer
An
edge
modification
displacing
marginal
BiOCl
Bi2O3
proposed
construct
heterojunction,
promoting
ultrathin
nanosheets
exfoliation
due
enhanced
affinity
with
H2O.
spontaneously
aligning
Fermi
levels
mediate
a
built-in
electric
field-guided
Z-scheme
retard
recombination,
improve
redox
potentials.
Hence,
these
high-powered
capable
catalyzing
diverse
stable
substrates,
such
as
reduction
reactions,
O2
→
·O2-
CO2
CO,
oxidation
GSH
GSSG
H2O
·OH.
extending
completely
breaks
tumor
microenvironment
limitation,
exhibiting
high
anticancer
activity.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(12), С. 6658 - 6670
Опубликована: Фев. 21, 2023
Developing
efficient
and
simple
catalysts
to
reveal
the
key
scientific
issues
in
epoxidation
of
ethylene
has
been
a
long-standing
goal
for
chemists,
whereas
heterogenized
molecular-like
catalyst
is
desirable
which
combines
best
aspects
homogeneous
heterogeneous
catalysts.
Single-atom
can
effectively
mimic
molecular
on
account
their
well-defined
atomic
structures
coordination
environments.
Herein,
we
report
strategy
selective
ethylene,
exploits
comprising
iridium
single
atoms
interact
with
reactant
molecules
that
act
analogously
ligands,
resulting
catalysis.
This
catalytic
protocol
features
near-unity
selectivity
(99%)
produce
value-added
oxide.
We
investigated
origin
improvement
oxide
this
single-atom
attributed
π-coordination
between
metal
center
higher
oxidation
state
or
oxygen.
The
oxygen
adsorbed
site
not
only
helps
strengthen
adsorption
molecule
by
but
also
alters
its
electronic
structure,
allowing
donate
electrons
into
double
bond
π*
orbitals
ethylene.
facilitates
formation
five-membered
oxametallacycle
intermediates,
leading
exceptionally
high
Our
model
featuring
remarkable
catalysis
be
utilized
as
an
effective
inhibiting
overoxidation
desired
product.
Implementing
concepts
would
provide
new
perspectives
design
advanced
