Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(24), P. 4459 - 4463
Published: June 13, 2022
Herein
we
report
C(sp2)-S
cross-coupling
reactions
of
aryl
iodides
and
arylsulfonyl
hydrazides
under
ligand-enabled,
Au(I)/Au(III)
redox
catalysis.
This
strategy
operates
mild
reaction
conditions,
requires
no
prefunctionalized
coupling
partner,
works
across
several
iodides.
The
utility
this
protocol
is
highlighted
through
the
synthesis
various
medicinally
relevant
biaryl
sulfones.
mechanism
supported
with
control
experiments,
mass
spectrometry,
NMR
studies.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(16), P. 8810 - 8816
Published: April 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,
Journal Year:
2024,
Volume and Issue:
146(6), P. 3660 - 3674
Published: Feb. 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.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(27)
Published: April 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,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 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,
Journal Year:
2020,
Volume and Issue:
59(29), P. 11808 - 11813
Published: March 23, 2020
Herein,
we
disclose
the
gold-catalyzed
1,2-diarylation
of
alkenes
through
interplay
ligand-enabled
AuI
/AuIII
catalysis
with
idiosyncratic
π-activation
mode
gold
complexes.
Unlike
classical
migratory-insertion-based
approach
to
1,2-diarylation,
present
not
only
circumvents
formation
direct
Ar-Ar'
coupling
and
Heck-type
side
products
but
more
intriguingly
demonstrates
reactivity
selectivity
complementary
those
previously
known
metal
(Pd,
Ni,
or
Cu).
Detailed
investigations
underpin
mechanistic
scenario
revealed
oxidative
addition
aryl
iodides
an
complex
be
rate-limiting
step
owing
non-innocent
nature
alkene.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(38), P. 16625 - 16630
Published: May 21, 2020
Abstract
Heteroarylation
of
alkenes
with
aryl
iodides
was
efficiently
achieved
a
(MeDalphos)AuCl
complex
through
Au
I
/Au
III
catalysis.
The
possibility
to
combine
oxidative
addition
and
π‐activation
at
gold
is
demonstrated
for
the
first
time.
reaction
robust
general
(>30
examples
including
internal
alkenes,
5‐,
6‐,
7‐membered
rings).
It
regioselective
leads
exclusively
trans
products.
(P,N)
most
efficient
electron‐rich
substrates,
which
are
troublesome
alternative
photoredox/oxidative
approaches.
In
addition,
it
provides
very
unusual
switch
in
regioselectivity
from
5‐
exo
6‐
endo
cyclization
between
Z
E
isomers
alkenols.
Organic Letters,
Journal Year:
2019,
Volume and Issue:
21(19), P. 8101 - 8105
Published: Sept. 26, 2019
The
first
example
of
ancillary
(P,N)-ligand-enabled
gold-catalyzed
C–N
cross-coupling
reactions
aryl
iodides
with
amines
is
reported.
high
generality
the
reaction
in
de
novo
synthesis,
late-stage
modifications,
and
cascade
processes
to
access
functionalized
indolinones
carbazoles
underscores
synthetic
potential
presented
strategy.
Monitoring
ESI-HRMS
NMR
provided
strong
evidence
for
situ
formation
putative
valent
Au(III)
intermediates.
European Journal of Inorganic Chemistry,
Journal Year:
2021,
Volume and Issue:
2021(26), P. 2556 - 2569
Published: May 19, 2021
Abstract
Oxidant‐free
Au(I)/Au(III)
catalysis
can
still
be
regarded
as
a
young
and
promising
chemistry.
Because
the
first
examples
of
gold
were
limited
to
activation
functionalization
π‐C−C
bonds
very
little
was
known
on
fundamental
organometallic
transformations
at
gold,
countless
works
during
past
15
years
have
been
devoted
disclosing
elementary
reactivity
implementing
it
in
catalysis.
Remarkably,
great
emphasis
triggering
oxidative
addition
Au(I)
has
placed,
high
redox
potential
pair
disfavors
this
reaction.
In
fact,
different
strategies
such
strain
release,
ligand
design
photochemistry
proven
successful
allowing
bottleneck
occur.
These
approaches
led
rational
development
oxidant‐free
catalysis,
particularly
catalytic
cycles
cross‐coupling
where
is
usually
entry
point
cycle.
Herein,
background
story,
process,
relevant
gold‐catalyzed
reactions
are
reviewed.
