Chemistry - A European Journal,
Год журнала:
2022,
Номер
28(17)
Опубликована: Фев. 10, 2022
The
first
chiral
helicene-NHC
gold(I)
complexes
efficient
in
enantioselective
catalysis
were
prepared.
L-shaped
ligand
is
composed
of
an
imidazo[1,5-a]pyridin-3-ylidene
(IPy)
scaffold
laterally
substituted
by
a
configurationally
stable
[5]-helicenoid
unit.
information
was
introduced
key
post-functionalization
step
NHC-gold(I)
complex
bearing
symmetrical
anionic
fluoreno[5]helicene
substituent,
leading
to
racemic
mixture
featuring
three
correlated
elements
chirality,
namely
central,
axial
and
helical
chirality.
After
HPLC
enantiomeric
resolution,
X-ray
crystallography
theoretical
calculations
enabled
structural
stereochemical
characterization
these
complexes.
high
potential
asymmetric
demonstrated
the
benchmark
cycloisomerization
N-tethered
1,6-enynes
with
up
95
:
5
er.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(22)
Опубликована: Фев. 27, 2023
Abstract
The
discovery
of
the
medicinal
properties
gold
complexes
has
fuelled
design
and
synthesis
new
anticancer
metallodrugs,
which
have
received
special
attention
due
to
their
unique
modes
action.
Current
research
in
development
compounds
with
therapeutic
is
predominantly
focused
on
molecular
drug
leads
superior
pharmacological
activities,
e.g.,
by
introducing
targeting
features.
Moreover,
intensive
aims
at
improving
physicochemical
compounds,
such
as
chemical
stability
solubility
physiological
environment.
In
this
regard,
encapsulation
nanocarriers
or
grafting
onto
targeted
delivery
vectors
could
lead
nanomedicines
that
eventually
reach
clinical
applications.
Herein,
we
provide
an
overview
state‐of‐the‐art
progress
andmore
importantly
thoroughly
revise
nanoparticle‐based
systems
for
chemotherapeutics.
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.
Arylation
of
gold
holds
paramount
importance
in
the
domain
organometallic
chemistry;
however,
exploration
arylgold
nanoclusters
remains
its
infancy
primarily
due
to
synthetic
challenge.
Here,
we
present
a
facile
and
effective
arylation
strategy
directly
synthesize
two
(
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 6, 2025
Luminescent
gold(I)
compounds
have
attracted
intensive
attention
due
to
anticipated
strong
spin-orbit
coupling
(SOC)
resulting
from
heavy
atom
effect
of
gold
atoms.
However,
some
mononuclear
are
barely
satisfactory.
Here,
we
unveil
that
low
participation
in
transition-related
orbitals,
caused
by
6s-π
symmetry
mismatch,
is
the
cause
SOCs
monogold(I)
compounds.
To
address
this
issue,
developed
a
series
acceptor-donor
organogold(I)
luminescent
incorporating
gem-digold
moiety
with
various
aryl
donors.
These
demonstrate
wide-range
tunable
emission
colors
and
impressive
photoluminescence
quantum
yields
up
78%,
among
highest
reported
for
polynuclear
We
further
reveal
integration
allows
better
interaction
6s
orbitals
π
facilitates
aryl-to-gold
electron
transfer,
reduces
Pauli
repulsion
between
digold
units,
finally
engendering
formation
aurophilic
interaction-based
aggregates.
Moreover,
strength
such
intermolecular
can
be
systematically
regulated
donor
nature
ligands.
The
those
aggregates
significantly
enhances
SOC
<10
239
cm−1
mainly
accounts
high-efficiency
phosphorescent
solid
state.
Some
unexpectedly
weak
coupling,
thus
limiting
their
phosphorescence
efficiency.
authors
develop
organodigold(I)
investigate
relationship
structures,
interaction,
coupling.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(40)
Опубликована: Авг. 6, 2022
Abstract
The
practical
use
of
luminescent
mononuclear
gold(I)
complexes
as
optoelectronic
materials
has
been
limited
by
their
inferior
stability.
Herein
we
demonstrate
a
strategy
to
improve
the
stability
which
display
thermally
activated
delayed
fluorescence
(TADF).
A
highly
rigid
and
groove‐like
σ‐donating
aryl
ligand
used
form
dual
Au⋅⋅⋅H−C
hydrogen
bonds.
secondary
metal‐ligand
interactions
have
authenticated
single‐crystal
structure,
NMR
spectroscopy
theoretical
simulations.
TADF
Au
I
complex
exhibits
appealing
emission
properties
(photoluminescence
quantum
yield=76
%;
lifetime=1.2
μs)
much
improved
thermal
photo‐stability.
Vacuum‐deposited
organic
light‐emitting
diodes
(OLEDs)
show
promising
electroluminescence
with
maximum
external
efficiency
(EQE)
over
23
%
negligible
roll‐off
even
at
10
000
cd
m
−2
.
An
estimated
LT
50
longer
than
77
h
initial
luminance
100
reveals
good
operational
This
work
suggests
way
for
design
stable
complexes.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(41), С. 22720 - 22727
Опубликована: Окт. 4, 2023
Construction
of
gold-based
metal-organic
frameworks
(Au-MOFs)
would
bring
the
merits
gold
chemistry
into
MOFs.
However,
it
still
remains
challenging
because
cations
are
easily
reduced
to
metallic
under
solvothermal
conditions.
Herein,
we
present
first
example
Au-MOFs
prepared
from
networking
cyclic
trinuclear
gold(I)
complexes
by
formal
transimination
reaction
in
a
rapid
(<15
min)
and
scalable
(up
1
g)
fashion
ambient
condition.
The
feature
uniform
porosity,
high
crystallinity,
superior
chemical
stability
toward
base
(i.e.,
20
M
NaOH).
With
open
Au(I)
sites
skeleton,
as
heterogeneous
catalysts
delivered
good
performance
substrate
tolerance
for
carboxylation
reactions
alkynes
with
CO2.
This
work
demonstrates
facile
approach
reticularly
synthesize
combining
coordination
dynamic
covalent
chemistry.
ACS Catalysis,
Год журнала:
2023,
Номер
13(13), С. 8845 - 8860
Опубликована: Июнь 20, 2023
Despite
the
unique
position
of
gold
catalysis
in
contemporary
organic
synthesis,
this
area
research
is
notorious
for
requiring
activators
and/or
additives
that
enable
by
generating
cationic
forms
catalysts.
Cycloisomerization
reactions
occupy
a
significant
portion
gold-catalyzed
reaction
space,
while
they
represent
diverse
family
are
frequently
utilized
synthesis.
Herein,
hexafluoroisopropanol
(HFIP)
shown
to
be
uniquely
simple
tool
cycloisomerizations,
rendering
use
external
obsolete
and
leading
highly
active
catalytic
systems
with
ppm
levels
catalyst
loading
certain
cases.
HFIP
assumes
dual
role
as
solvent
an
activator,
operating
via
dynamic
activation
Au–Cl
bond
through
hydrogen
bonding,
which
initiates
cycle.
This
special
mode
can
efficient
scalable
cyclization
propargylamides
ynoic
acids
[AuCl(L)]
complexes.
A
thorough
screening
ancillary
ligands
counter
anions
has
been
performed,
establishing
methodology
alternative
elaborate
ligand/catalyst
design
activators.
Additionally,
concept
applied
C–C
bond-forming
cycloisomerization
2H-chromenes
sequential
or
one-pot
transformations
activated
ketoesters,
functionalized
N-heterocyclic
carbene
(NHC)
precursor
salt,
compound
bearing
bioactive
indole
core,
among
others.
Importantly,
mechanistic
investigations,
including
"snapshot"
species
interest
solid
state,
we
were
able
unambiguously
detect
key
H-bonding
interaction
between
catalyst,
shedding
light
on
intermolecular
enables
catalysis.
In
cases
examined
herein,
not
only
excellent
but
also
potent
activator
valuable
synthetic
handle
when
incorporated
into
functional
groups
products.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(6), С. 1858 - 1895
Опубликована: Янв. 1, 2024
This
review
is
planned
to
provide
a
comprehensive
overview
of
the
progress
made
in
design
and
development
chiral
ligands
for
asymmetric
gold
catalysis.
ACS Catalysis,
Год журнала:
2022,
Номер
12(7), С. 4046 - 4053
Опубликована: Март 16, 2022
Gold(I)
complexes
of
a
chiral
phosphoric
acid-functionalized
phosphine
the
CPA-Phos
series
enable
enantioselective
multicomponent
reactions
between
aldehydes,
hydroxylamines
and
cyclic
yne-enones,
leading
to
3,4-dihydro-1H-furo[3,4-d][1,2]oxazines.
This
represents
rare
example
highly
reaction
in
gold(I)
catalysis.
The
proceed
at
low
catalyst
loading
provide
high
yields,
total
diastereoselectivity,
enantiomeric
excesses
up
99%.
Silver-free
conditions
can
be
applied.
method
has
very
broad
scope
as
it
applies
both
aliphatic
aromatic
aldehydes
hydroxylamines,
variety
yne-enone-derived
oximes.
DFT
calculations
complement
this
study
enlighten
reactivity
issues
mechanistic
pathways.