Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: May 21, 2024
Abstract
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,
31
P
NMR
and
DFT
studies
performed
underpin
mechanism.
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:
2024,
Volume and Issue:
146(18), P. 12365 - 12374
Published: April 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.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: May 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,
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(47)
Published: Aug. 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.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 28, 2025
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.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(20), P. 5731 - 5740
Published: Jan. 1, 2024
A
simple
and
practical
method
for
the
synthesis
of
S
-alkyl
phosphorothioates/phosphorodithioates
through
three-component
reaction
cyclic
sulfonium
salts
with
8
,
H
-phosphonates,
or
P
4
10
alcohols
was
readily
developed.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(43), P. 9413 - 9418
Published: Oct. 18, 2024
A
gold-catalyzed
sulfonylation
reaction
of
aryl
iodides
with
different
sodium
sulfinates
facilitated
by
the
ligand-enabled
Au(I)/Au(III)
redox
catalysis
was
developed.
In
C–S
coupling,
a
variety
functionalized
sulfinates,
such
as
CF3,
CHF2,
CH3,
and
alkyl
groups,
can
react
smoothly
to
directly
construct
diversely
sulfones.
This
offers
complementary
method
for
synthesizing
sulfones
electron-donating
groups.
