Angewandte Chemie,
Год журнала:
2024,
Номер
137(1)
Опубликована: Ноя. 12, 2024
Abstract
We
recently
reported
the
gold‐catalyzed
Heck
and
chain‐walking
reactions,
which
utilize
migratory
insertion,
β
‐hydride
elimination
steps
in
a
catalytic
fashion.
Budzelaar
et
al.
their
correspondence
state
that
these
reactions
proceed
through
alkene
heteroarylation
followed
by
acid‐mediated
cyclization
sequence.
In
response
to
this
correspondence,
we
have
conducted
some
experiments
convinced
us
product
formation
solely
can
not
be
rationalized
based
on
hetero‐arylation
of
alkenes
under
ligand‐enabled
Au(I)/Au(III)
catalysis.
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.
Herein,
we
report
the
gold-catalyzed
deallylative
C-S
cross-coupling
reaction
through
ligand-enabled
Au(I)/Au(III)
redox
catalysis.
One
of
major
challenges
in
reactions
is
to
prevent
catalyst
deactivation
caused
by
formation
a
strong
gold-sulfur
bond.
We
discovered
that
use
allyl
phenyl
sulfide
as
sulfur
surrogate
facilitates
dynamic
equilibrium
between
cationic
Au(I)
and
Au(I)-sulfide
complexes,
overcoming
gold
quenching
problem.
A
detailed
mechanistic
investigation,
including
31P
NMR
studies,
mass
analysis,
stoichiometric
experiments,
provided
valuable
insights
into
mechanism,
which
further
supported
computational
studies.
A
selectivity-control
approach
for
palladium-catalyzed
dearomative
para-/ortho-cycloaddition
cascades
of
aromatic
compounds
with
1,4-enynes
and
CO
via
a
skeletal
reorganization
process
to
produce
polycycle-fused
bicyclo[2.2.2]octenes
is
reported.
This
mechanistically
novel
depends
on
that
consists
sequence
[4
+
2]
para-cycloaddition,
3,3-Cope
rearrangement,
carbon–carbon
bond
activation/[4
cycloaddition.
1,2-Migration
on
arenes
represents
a
powerful
transformation,
because
of
its
chemical
skeleton
and
exit
vector
editing
ability.
However,
the
corresponding
dearomative
mediated
1,2-migration
arene
was
ignored
for
decades,
despite
tremendous
effort
being
devoted
to
develop
reaction,
which
mainly
capitalized
breaking
planarity
three-dimensional
diversification.
Here,
we
report
gold-catalyzed
1,2-rearrangement
benzene
by
transient
dearomatization
high-resonance
energy
benzene.
This
functional
transposition
strategy
enabled
rapid
access
several
precursors
extended
π-conjugated
molecules,
showcasing
potential
applications
in
materials
sciences.
Chemistry - An Asian Journal,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 28, 2025
Abstract
Gold
catalysis
has
witnessed
remarkable
advances
over
the
past
decade,
with
numerous
insightful
reviews
chronicling
this
progress.
However,
a
comprehensive
review
addressing
developments
in
field
during
post‐pandemic
COVID
era
remains
notably
absent.
This
aims
to
bridge
that
gap
by
providing
an
in‐depth
analysis
of
recent
studies,
shedding
light
on
unique
properties
gold
complexes,
particularly
intriguing
aurophilic
interactions
distinguish
chemistry.
The
systematically
explores
latest
achievements
both
mono‐
and
dinuclear
gold‐catalyzed
reactions,
focus
their
applications
diverse
fields,
including
redox
coupling,
asymmetric
catalysis,
photo‐,
electrocatalysis.
A
special
emphasis
is
placed
comparative
performance
catalysts,
latter
often
exhibiting
enhanced
catalytic
efficiency
selectivity
certain
reactions.
By
integrating
mechanistic
insights
DFT
perspectives
representative
experimental
studies
from
years,
highlights
significance
synthetic
chemistry,
identifies
emerging
trends
outlines
future
directions
for
field.
Herein,
for
the
first
time,
we
disclose
migratory
insertion
of
alkynes
into
Au(III)‒C
bonds
in
a
catalytic
fashion.
Experimental
results
clearly
suggest
that
pathway
predominates
over
π-activation
-
finding
further
supported
by
Density
Functional
Theory
(DFT)
calculations.
The
observed
regioselectivity
underscores
distinct
advantages
and
complementarity
gold
catalysis
comparison
to
palladium
catalysis.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
64(1)
Опубликована: Ноя. 12, 2024
Abstract
We
recently
reported
the
gold‐catalyzed
Heck
and
chain‐walking
reactions,
which
utilize
migratory
insertion,
β
‐hydride
elimination
steps
in
a
catalytic
fashion.
Budzelaar
et
al.
their
correspondence
state
that
these
reactions
proceed
through
alkene
heteroarylation
followed
by
acid‐mediated
cyclization
sequence.
In
response
to
this
correspondence,
we
have
conducted
some
experiments
convinced
us
product
formation
solely
can
not
be
rationalized
based
on
hetero‐arylation
of
alkenes
under
ligand‐enabled
Au(I)/Au(III)
catalysis.
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.
