Organometallics,
Год журнала:
2024,
Номер
43(21), С. 2831 - 2842
Опубликована: Окт. 29, 2024
Arylation
of
Y–H
bonds
(Y
=
N,
C,
O,
S)
catalyzed
by
transition
metal
complexes
typically
requires
an
external
base
to
deprotonate
the
bonds,
thereby
preparing
system
for
Y-aryl
coupling.
However,
designing
catalytic
reactions
that
operate
without
bases
is
preferred
due
benefits
such
as
simplicity,
cost
savings,
and
reduced
environmental
impact.
In
this
study,
we
demonstrate
substrates
with
can
undergo
Y-arylation
under
base-free
conditions
if
their
coordination
center
renders
them
sufficiently
acidic
deprotonation
solvent.
We
identified
several
reports
in
literature
meet
criterion,
including
arylation
anilines
1,3,5-trimethoxybenzene
using
hemilabile
ligand-enabled
Au(I)/Au(III)
catalysis
methanol.
Our
density
functional
theory
(DFT)
calculations
reveal
key
intermediate
Au(III)-substrate
adduct.
The
success
depends
on
acidity
(pKa)
adduct,
which
significantly
influenced
substrate
substituents.
For
example,
our
indicate
pKa
values
Au(III)-coordinated
p-nitroaniline
methanol
are
2.1
4.6,
respectively.
These
adducts
thus
be
easily
deprotonated
solvent,
enabling
conditions.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(27)
Опубликована: Апрель 30, 2024
Abstract
In
this
minireview
we
survey
the
challenges
and
strategies
in
gold
redox
catalysis.
Gold's
reluctance
to
oxidative
addition
reactions
due
its
high
potential
limits
applicability.
Initial
attempts
overcome
problem
focused
on
use
of
sacrificial
external
oxidants
stoichiometric
amounts
bring
Au(I)
compounds
Au(III)
reactive
species.
Recently,
innovative
approaches
employing
hemilabile
ligands,
which
are
capable
coordinating
stabilizing
square‐planar
intermediates,
thus
facilitating
steps
enabling
oxidant‐free
Notable
examples
include
(P^N)
bidendate
MeDalphos
ligand
achieve
various
cross‐coupling
via
Au(I)/Au(III).
Importantly,
ligand‐enabled
catalysis
allows
merging
with
π‐activation,
such
as
oxy‐
aminoarylation
alkenols
alkenamines
using
organohalides,
expanding
gold‘s
versatility
C−C
C‐heteroatom
bond
formations
unprecedented
cyclizations.
Moreover,
recent
advancements
enantioselective
chiral
ligands
also
surveyed.
Strikingly,
versatile
bidentate
(C^N)
competitors
have
appeared
recently,
by
designing
scaffolds
where
phosphine
groups
substituted
N‐heterocyclic
or
mesoionic
carbenes.
Overall,
these
highlight
evolving
landscape
tremendous
a
broad
scope
transformations.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(18), С. 12365 - 12374
Опубликована: Апрель 24, 2024
Through
mechanistic
work
and
rational
design,
we
have
developed
the
fastest
organometallic
abiotic
Cys
bioconjugation.
As
a
result,
Au(III)
bioconjugation
reagents
enable
selective
labeling
of
moieties
down
to
picomolar
concentrations
allow
for
rapid
construction
complex
heterostructures
from
peptides,
proteins,
oligonucleotides.
This
showcases
how
chemistry
can
be
interfaced
with
biomolecules
lead
range
reactivities
that
are
largely
unmatched
by
classical
organic
tools.
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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Май 21, 2024
Cope
rearrangements
have
garnered
significant
attention
owing
to
their
ability
undergo
structural
reorganization
in
stereoselective
manner.
While
substantial
advances
been
achieved
over
decades,
these
remained
applicable
exclusively
parent
1,5-hexadienes.
Herein,
we
disclose
the
gold-catalyzed
arylative
rearrangement
of
1,6-heptadienes
via
a
cyclization-induced
[3,3]-rearrangement
employing
ligand-enabled
gold
redox
catalysis.
Detailed
mechanistic
investigations
including
several
control
experiments,
cross-over
experiment,
HRMS
analysis,
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
In
silico
examination
of
13
P
,
N
-ligated
Au(
iii
)
OACs
determined
the
key
mechanistic
factors
governing
)-mediated
S
-arylation.
Three
complexes
were
synthesized
which
exhibited
bimolecular
coordination
rate
constants
as
high
20
200
M
−1
s
.
Abstract
The
high
oxidation
potential
of
Au(I)/Au(III)
redox
couple
renders
the
development
gold‐catalyzed
cross‐coupling
reactions
highly
challenging.
In
pursuit
catalysis,
various
strategies,
such
as
use
stoichiometric
oxidants,
merged
gold/photoredox
systems,
or
ligand‐enabled
approaches,
have
been
adopted
to
achieve
Au(I)
Au(III)
complexes.
Recently,
electrochemical
anodic
oxidation‐based
gold
catalysis
has
emerged
a
new
technique
facilitate
reactions.
This
concept
article
provides
succinct
overview
highlighting
challenges
and
future
developments.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(47)
Опубликована: Авг. 12, 2024
Abstract
Herein,
we
disclose
the
first
report
on
gold‐catalyzed
C(sp
2
)‐CN
cross‐coupling
reaction
by
employing
a
ligand‐enabled
Au(I)/Au(III)
redox
catalysis.
This
transformation
utilizes
acetone
cyanohydrin
as
nucleophilic
cyanide
source
to
convert
simple
aryl
and
alkenyl
iodides
into
corresponding
nitriles.
Combined
experimental
computational
studies
highlighted
crucial
role
of
cationic
silver
salts
in
activating
stable
(P,N)‐AuCN
complex
towards
oxidative
addition
subsequently
generate
key
aryl‐Au(III)
complexes.
Herein,
we
disclose
an
unprecedented
gold-catalyzed
1,2-carboxyarylation
of
alkenes
through
ligand-enabled
Au(I)/Au(III)
catalysis.
Unlike
other
approaches
for
the
arylative
functionalization
C-C
multiple
bonds,
attempts
to
utilize
weak
nucleophiles
such
as
carboxylate
anions
were
unsuccessful.
The
key
achieving
this
transformation
is
use
a
1,3-diketone-appended
alkene,
which
undergoes
oxyarylation
followed
by
retro-aldol
reaction
afford
product.
Detailed
mechanistic
investigations
conducted
support
proposed
mechanism.
Herein,
we
report
17
new
(P^N)
ligands
for
redox
gold
catalysis,
featuring
various
substituents
at
-C4,
-C5,
and
-C6
of
the
aryl
ring
nitrogen
handle.
Rate
kinetics
experiments
revealed
that
electron-rich
-C4
-C5
positions
enhanced
rate
oxidative
addition
Au(I)
with
C(sp2)-Br
bonds
compared
to
electron-poor
substituents.
Further,
an
unprecedented
gold-catalyzed
arylation
aliphatic
amines
using
electronically
rich
ligand
(L6)
-OMe
group
position.
