Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(20), P. 3766 - 3771
Published: May 11, 2023
Alkyldiarylsulfonium
salts
were
synthesized
by
a
combination
of
active
sulfonium
species,
prepared
through
the
activation
diarylsulfoxide,
and
alkyl
nucleophiles.
The
isolated
subjected
to
allylation
cyclopropanation
methylene
compounds
metal-free
C(sp3)-C(sp2)
couplings
via
oxyallyl
cation
intermediates
under
mild
conditions.
series
reactions
included
an
umpolung
strategy
for
coupling
nucleophiles
C-C
bond
formation
using
salts.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(16), P. 4464 - 4469
Published: Jan. 1, 2024
A
visible-light-induced
oxytrifluoromethylation
reaction
of
carbamate-containing
alkenes
has
been
reported
for
the
synthesis
diverse
cyclic
carbonates
and
vicinal
diols
bearing
trifluoroethyl
substituted
quaternary
centers.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(23), P. 6660 - 6665
Published: Jan. 1, 2024
A
photocatalyst-free
method
enables
efficient
alkene
difunctionalization
in
CF
3
-rich
organic
environments
using
accessible
starting
materials.
This
protocol
is
applicable
for
the
synthesis
of
alkoxy,
hydroxy,
and
azido
derivatives.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 18, 2024
Nucleophilic
addition
to
α,β-unsaturated
carbonyl
compounds
normally
occurs
at
the
carbon
or
β-carbon.
The
direct
α-nucleophilic
α-carbon
can
hardly
be
achieved
due
electronic
mismatch.
In
this
work,
we
report
nucleophilic
of
β-fluoroalkyl
α-carbonyl
carbocations
that
are
prepared
via
CBZ6-induced
redox-neutral
photocatalysis.
process,
photocatalytic
oxidation
radical
corresponding
carbocation
is
key
step.
generated
in
situ
by
a
polyfluoroalkyl
radical,
which
fragmentation
sulfonyl
chloride,
carbonyls.
high
E00
value
CBZ6
(3.19
V
vs
saturated
calomel
electrode),
corresponds
with
absorbed
photoenergy,
contributes
catalytic
reactivity.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(49)
Published: Oct. 19, 2023
α-Carbonyl
cations
are
the
umpolung
forms
of
synthetically
fundamental
α-carbonyl
carbanions.
They
highly
reactive
yet
rarely
studied
and
utilized
species
their
precursors
were
rather
limited.
Herein,
we
report
catalyst-controlled
divergent
generations
from
single
alkyne
functionalities
interception
them
via
Wagner-Meerwein
rearrangement.
Two
chemodivergent
catalytic
systems
have
been
established,
leading
to
two
different
types
and,
eventually,
products,
i.e.
α,β-
β,γ-unsaturated
carbonyl
compounds.
Broad
spectrum
alkynes
including
aryl
alkyne,
ynamide,
alkynyl
ether,
sulfide
could
be
migration
priorities
groups
in
rearrangement
step
was
elucidated.
Density
functional
theory
calculations
further
supported
intermediacy
N-O
bond
cleavage
both
systems.
Another
key
feature
this
methodology
fragmentation
inert
tert-butyl
into
readily
transformable
olefin
functionalities.
The
synthetic
potential
highlighted
by
scale-up
reactions
downstream
diversifications
formal
synthesis
nicotlactone
B
galbacin.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(20), P. 3766 - 3771
Published: May 11, 2023
Alkyldiarylsulfonium
salts
were
synthesized
by
a
combination
of
active
sulfonium
species,
prepared
through
the
activation
diarylsulfoxide,
and
alkyl
nucleophiles.
The
isolated
subjected
to
allylation
cyclopropanation
methylene
compounds
metal-free
C(sp3)-C(sp2)
couplings
via
oxyallyl
cation
intermediates
under
mild
conditions.
series
reactions
included
an
umpolung
strategy
for
coupling
nucleophiles
C-C
bond
formation
using
salts.
