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.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(14), P. 8478 - 8558
Published: Feb. 8, 2021
The
catalyst-directed
divergent
synthesis,
commonly
termed
as
"divergent
catalysis",
has
emerged
a
promising
technique
it
allows
chartering
of
structurally
distinct
products
from
common
substrates
simply
by
modulating
the
catalyst
system.
In
this
regard,
gold
complexes
powerful
catalysts
they
offer
unique
reactivity
profiles
compared
to
various
other
transition
metal
catalysts,
primarily
due
their
salient
electronic
and
geometrical
features.
Owing
tunable
soft
π-acidic
nature,
not
only
evolved
superior
contenders
for
catalyzing
reactions
alkynes,
alkenes,
allenes
but
also,
more
intriguingly,
have
been
found
provide
reaction
pathways
over
π-acid
such
Ag,
Pt,
Pd,
Rh,
Cu,
In,
Sc,
Hg,
Zn,
etc.
recent
past
witnessed
renaissance
in
examples
wherein,
choosing
or
fine-tuning
ligands,
counteranions
oxidation
states
itself,
complete
switch
was
observed.
However,
reviews
documenting
are
sporadic;
result,
most
reports
kind
remained
scattered
literature,
thereby
hampering
further
development
burgeoning
field.
By
conceptualizing
idea
"Divergent
Gold
Catalysis
(DGC)",
review
aims
consolidate
all
unified
approach
necessary
pave
way
advancement
exciting
area.
Based
on
factors
governing
divergence
product
formation,
an
explicit
classification
DGC
provided.
To
gain
fundamental
understanding
observed
reactivities
selectivities,
is
accompanied
mechanistic
insights
at
appropriate
places.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
121(14), P. 8364 - 8451
Published: Sept. 23, 2020
Over
the
past
decade
organometallic
chemistry
of
gold(III)
has
seen
remarkable
advances.
This
includes
synthesis
first
examples
several
compound
classes
that
have
long
been
hypothesized
as
being
part
catalytic
cycles,
such
alkene,
alkyne,
CO
and
hydride
complexes,
important
catalysis-relevant
reaction
steps
at
last
demonstrated
for
gold,
like
migratory
insertion
β-H
elimination
reactions.
Also,
pathways
were
already
known,
example
generation
intermediates
by
oxidative
addition
their
reductive
elimination,
are
much
better
understood.
A
deeper
understanding
fundamental
reactivity
revealed
unexpected
mechanistic
avenues,
which
can
open
when
barriers
reactions
other
metals
would
be
regarded
"standard"
too
high.
review
summarizes
evaluates
these
developments,
together
with
applications
in
catalysis,
emphasis
on
insight
gained
investigations.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(18), P. 10422 - 10450
Published: Jan. 1, 2021
This
review
highlights
a
decade-long
journey
of
Au-catalyzed
1,2-difunctionalization
reactions
C–C
multiple
bonds
that
have
been
realized
due
to
the
productive
integration
Au(
i
)/Au(
iii
)catalysis
with
unique
π-activation
mode
gold
complexes.
Organic Chemistry Frontiers,
Journal Year:
2021,
Volume and Issue:
8(18), P. 5206 - 5228
Published: Jan. 1, 2021
Various
alkene
difunctionalization
reactions
involving
nitridization,
diamination,
azidation,
oxyamination,
carboamination,
aminohalogenation,
and
nitration
are
introduced
in
this
review.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(16), P. 7089 - 7095
Published: April 18, 2022
Presented
herein
is
the
first
report
of
enantioselective
Au(I)/Au(III)
redox
catalysis,
enabled
by
a
newly
designed
hemilabile
chiral
(P,N)-ligand
(ChetPhos).
The
potential
this
concept
has
been
demonstrated
development
1,2-oxyarylation
and
1,2-aminoarylation
alkenes
which
provided
direct
access
to
medicinally
relevant
3-oxy-
3-aminochromans
(up
88%
yield
99%
ee).
DFT
studies
were
carried
out
unravel
enantiodetermining
step,
revealed
that
stronger
trans
influence
phosphorus
allows
selective
positioning
substrate
in
C2-symmetric
environment
present
around
nitrogen,
imparting
high
level
enantioselectivity.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(12)
Published: Jan. 21, 2022
Abstract
The
first
C−SCF
3
/SeCF
cross‐coupling
reactions
using
gold
redox
catalysis
[(MeDalphos)AuCl],
AgSCF
or
Me
4
NSeCF
,
and
organohalides
as
substrates
are
reported.
new
methodology
enables
a
one‐stop
shop
synthesis
of
aryl/alkenyl/alkynyl
trifluoromethylthio‐
selenoethers
with
broad
substrate
scope
(>60
examples
up
to
97
%
isolated
yield).
method
is
scalable,
its
robustness
evidenced
by
the
late‐stage
functionalization
various
bioactive
molecules,
which
makes
this
reaction
an
attractive
alternative
in
for
pharmaceutical
agrochemical
research
development.
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
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(17)
Published: Feb. 24, 2023
Precisely
introducing
two
similar
functional
groups
into
bulk
chemical
alkenes
represents
a
formidable
route
to
complex
molecules.
Especially,
the
selective
activation
of
electrophiles
is
in
crucial
demand,
yet
challenging
for
cross-electrophile-coupling.
Herein,
we
demonstrate
redox-mediated
electrolysis,
which
aryl
nitriles
are
both
radical
precursors
and
redox-mediators,
enables
an
intermolecular
alkene
1,2-diarylation
with
remarkable
regioselectivity,
thereby
avoiding
involvement
transition-metal
catalysts.
This
transformation
utilizes
cyanoarene
anions
activating
various
halides
(including
iodides,
bromides,
even
chlorides)
affords
adducts
up
83
%
yield
>20
:
1
regioselectivity
more
than
80
examples,
providing
feasible
approach
bibenzyl
derivatives.
