Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 1, 2025
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.
Synlett,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 14, 2025
Abstract
The
catalytic
asymmetric
Friedel–Crafts
reactions
of
(hetero)arenes
represent
a
cornerstone
in
synthetic
chemistry
due
to
their
ability
efficiently
incorporate
aromatic
rings
into
complex
molecular
architectures.
This
account
presents
comprehensive
overview
recent
advancements
the
enantioselective
(hetero)arenes,
with
particular
focus
on
that
facilitate
introduction
multiple
C–C
bonds
via
iranium/irenium-ion-triggered
electrophilic
processes.
We
examine
detail
strategies
and
methodologies
employed
achieve
stereoselective
incorporation
unsaturated
bonds,
highlighting
construction
diverse
structural
scaffolds.
Additionally,
this
showcases
broad
range
applications
powerful
transformation
organic
synthesis.
1
Introduction
2
Catalytic
Enantioselective
Reactions
Thiiranium/Thiirenium
Ions
2.1
Arylthiiranium/Arylthiirenium-Ion-Triggered
2.2
Trifluoromethylthiiranium/Trifluoromethylthiirenium-Ion-Triggered
3
Haliranium
3.1
Chloriranium-Ion-Triggered
3.2
Bromiranium-Ion-Triggered
3.3
Iodiranium-Ion-Triggered
Asymmetric
Oxidative
Arylation
Alkenes
4
Conclusion
Outlook
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 15, 2025
A
new
family
of
ortho-hydroxy-substituted
diaryliodonium
salts
was
synthesized
with
1-acetoxy-2-iodobenzenes,
in
which
the
acetyl
group
cleaved
a
one-pot
synthesis.
The
ortho-hydroxyl-substituted
underwent
further
intramolecular
aryl
migration
reaction,
giving
ortho-iodo
diaryl
ethers
either
or
without
presence
bases.
Chinese Journal of Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 18, 2025
Comprehensive
Summary
An
innovative
visible‐light‐driven
direct
hydrogen
atom
transfer
(
d
‐HAT)
of
Ge–H
bond
has
been
developed,
wherein
the
photoexcited
9,10‐phenanthraquinone
PC
HAT
9
)
serves
as
an
efficient
photocatalyst
for
generation
germanium‐centered
radicals
from
germanium
hydrides
including
Ph
3
GeH,
n
Bu
and
2
GeH
.
By
employing
hypervalent
iodine
reagents
SOMOphiles,
this
protocol
facilitates
streamlined
germylation
through
a
mechanism
involving
germyl
radical
addition
followed
by
β‐cleavage
carboxyl
to
yield
diverse
array
ethynyl‐,
vinyl‐,
nitrile‐,
phenyl‐functionalized
germanes.
The
methodological
leap
signifies
noteworthy
departure
previous
photocatalytic
indirect
i
relying
on
combined
usage
SET
with
abstractors,
which
not
only
advances
methodology
creating
in
fashion
but
also
provides
access
structurally
novel
pharmaceutically
promising
organogermanium
compounds
that
are
difficult
synthesize
routine
methods.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 1, 2025
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.
