Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(40)
Published: Aug. 4, 2022
Abstract
An
asymmetric
para‐
C(sp
2
)−H
bond
functionalization
of
alkyl
benzene
derivatives
was
successfully
developed
via
cooperative
catalysis
gold
and
chiral
phosphoric
acid
(CPA),
leading
to
synthetically
useful
1,1‐diaryl
motifs.
Chiral
acid,
ligand,
molecular
sieves
were
found
be
crucial
for
enantioselectivity
control
this
transformation.
The
salient
features
protocol
include
mild
conditions,
high
efficiency,
commercially
available
starting
materials,
highly
chemo‐
site‐
as
well
enantioselective
aromatic
C−H
functionalization,
broad
substrate
scope,
extensive
applications
the
products.
mechanistic
studies
suggested
that
two
CPAs
might
involved
in
induction.
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.
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.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(6), P. 3847 - 3853
Published: March 3, 2023
Reported
herein
is
a
ligand-enabled
gold-catalyzed
C(sp2)–O
cross-coupling
reaction
of
aryl
iodides
and
aliphatic
alcohols.
The
synthesis
variety
alkyl
ethers
including
complex
biomolecules
various
medicinally
relevant
motifs
has
been
achieved
to
demonstrate
the
usefulness
method.
importance
gold
catalysis
highlighted
by
overcoming
selectivity
issues
that
are
in
general
observed
for
C–O
reactions
when
other
transition
metals
used
as
catalysts.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(27), P. 14865 - 14873
Published: June 28, 2023
The
amidated
peptides
are
an
important
class
of
biologically
active
compounds
due
to
their
unique
biological
properties
and
wide
applications
as
potential
peptide
drugs
biomarkers.
Despite
the
abundance
free
amide
motifs
(Asn,
Gln,
C-terminal
amide)
in
native
peptides,
late-stage
modification
unit
naturally
occurring
remains
very
rare
because
intrinsically
weak
nucleophilicity
amides
interference
multiple
competing
nucleophilic
residues,
which
generally
lead
undesired
side
reactions.
Herein,
chemoselective
arylation
unprotected
polypeptides
has
been
developed
under
air
atmosphere
afford
N-aryl
bearing
various
functional
motifs.
Its
success
relies
on
combination
gold
catalysis
silver
salt
differentiate
relative
inert
among
a
collection
reactive
amino
acid
residues
(e.g.,
-NH2,
-OH,
-COOH),
favoring
C-N
bond
coupling
toward
over
other
more
groups.
Experimental
DFT
studies
reveal
crucial
role
cation,
serves
transient
coordination
mask
reaction
sites,
overcoming
inherently
low
reactivity
amides.
excellent
biocompatibility
this
strategy
applied
functionalize
range
complex
peptides.
application
could
be
further
extended
labeling
stapling.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(9), P. 2359 - 2384
Published: Jan. 1, 2023
Multicomponent
reactions
(MCRs)
have
emerged
as
an
important
branch
in
organic
synthesis
for
the
creation
of
complex
molecular
structures.
This
review
is
focused
on
gold-catalyzed
MCRs
with
a
special
emphasis
recent
developments.