Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(37), С. 7618 - 7622
Опубликована: Янв. 1, 2024
A
novel
visible-light-driven
photoredox-catalyzed
cascade
bicyclization
of
1,7-enynes
with
aqueous
sulfoxonium
ylides
is
reported.
The
reaction
highly
chemoselective
three
new
C-C
bonds,
two
rings,
and
an
all-carbon
quaternary
stereocenter
constructed
in
a
one-pot
fashion.
This
mild
protocol
features
remarkably
broad
substrate
scope
good
functional
group
tolerance,
providing
general
practical
approach
to
access
various
cyclopenta[
JACS Au,
Год журнала:
2025,
Номер
5(2), С. 426 - 447
Опубликована: Янв. 29, 2025
Many
important
synthetic-oriented
works
have
proposed
excited
organic
radicals
as
photoactive
species,
yet
mechanistic
studies
raised
doubts
about
whether
they
can
truly
function
photocatalysts.
This
skepticism
originates
from
the
formation
of
(photo)redox-active
degradation
products
and
picosecond
decay
electronically
radicals,
which
is
considered
too
short
for
diffusion-based
photoinduced
electron
transfer
reactions.
From
this
perspective,
we
analyze
synthetic
transformations
where
been
photocatalysts,
comparing
their
theoretical
maximum
state
potentials
with
required
observed
photocatalytic
reactivity.
We
summarize
structurally
similar
photocatalysts
indicating
different
reaction
pathways
some
catalytic
systems,
addressing
cases
radical
exceed
Additionally,
perform
a
kinetic
analysis
to
explain
in
on
subpicosecond
time
scales.
further
rationalize
potential
anti-Kasha
reactivity
higher
states
femtosecond
lifetimes,
highlighting
how
future
photocatalysis
advancements
could
unlock
new
photochemical
pathways.
ACS Catalysis,
Год журнала:
2024,
Номер
14(2), С. 1193 - 1204
Опубликована: Янв. 9, 2024
Herein,
the
C3–H
alkylation
of
2H-indazoles
and
indoles
with
sulfoxonium
ylides
is
developed
under
visible-light
photocatalysis.
This
protocol
employs
easily
accessible
reagents,
a
wide
range
2H-indazoles,
indoles,
are
suitable
for
this
reaction
to
afford
desired
products
benign
conditions.
Synergistic
experimental
computational
studies
suggest
that
involving
photocatalysis
could
proceed
via
different
mechanistic
pathways.
For
C3-alkylation
triplet
energy
transfer
pathway
proposed
quenching
excited
photocatalyst.
Subsequently,
formed
state
undergo
radical
attack
on
C═S
moiety
ylides.
After
dissociation
DMSO
1,2-H
migration,
final
product
be
yielded.
However,
such
not
applicable
indoles.
Instead,
converted
C-centered
in
presence
KH2PO4
photoredox
The
can
C3-site
thus
lead
Organic Letters,
Год журнала:
2023,
Номер
25(23), С. 4286 - 4291
Опубликована: Июнь 2, 2023
Two
categories
of
tetrasubstituted
phenols
were
prepared
via
the
cycloaddition
reaction
vinyl
sulfoxonnium
ylides
with
cyclopropenones
in
a
switchable
manner.
Copper
carbenoid
was
proposed
as
active
intermediate
process
2,3,4,5-tetrasubstituted
formation,
while
2,3,5,6-tetrasubstituted
generated
direct
[3
+
3]
annulation
under
metal-free
conditions.
Further
synthetic
applications
also
demonstrated.
Molecules,
Год журнала:
2023,
Номер
28(7), С. 3027 - 3027
Опубликована: Март 28, 2023
Radical
transformations
are
powerful
in
organic
synthesis
for
the
construction
of
molecular
scaffolds
and
introduction
functional
groups.
In
radical
difunctionalization
reactions,
radicals
first
functionalized
intermediates
can
be
relocated
through
resonance,
hydrogen
atom
or
group
transfer,
ring
opening.
The
resulting
undertake
following
paths
second
functionalization:
(1)
couple
with
other
groups,
(2)
oxidize
to
cations
then
react
nucleophiles,
(3)
reduce
anions
electrophiles,
(4)
metal-complexes.
rearrangements
provide
opportunity
1,3-,
1,4-,
1,5-,
1,6-,
1,7-difunctionalization
products.
Multiple
ways
initiate
reaction
coupling
intermediate
make
reactions
good
at
remote
positions.
These
offer
advantages
synthetic
efficiency,
operation
simplicity,
product
diversity.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(11), С. 3234 - 3241
Опубликована: Янв. 1, 2024
Herein,
we
present
a
cascade
O–H
double
insertion
reaction
between
I
(III)
/S
(VI)
-ylides,
carboxylic
acids,
and
alcohols
under
metal-free
conditions,
enabling
the
modular
synthesis
of
unsymmetrical
α,α-
O
,
-substituted
ketones.
Organic Letters,
Год журнала:
2024,
Номер
26(27), С. 5811 - 5816
Опубликована: Июнь 28, 2024
A
practical
strategy
for
the
construction
of
diverse
phosphonyl
and
thiofunctionalized
sulfoxonium
ylides
via
controllable
monofunctionalization
hybrid
I(III)/S(VI)
is
presented.
This
process
allows
efficient
P–H
insertion
under
Cu
catalysis,
enabling
synthesis
ylides,
whereas
reaction
with
sulfur-containing
reagents
including
AgSCF3,
KSC(S)OR,
KSCN
mild
conditions
resulted
in
α-trifluoromethylthiolation,
dithiocarbanation,
thiocyanation
accordingly.
Of
note,
wide
substrate
compatibility
(108
examples),
excellent
efficiency
(up
to
99%
yield),
gram-scale
experiments,
various
product
derivatizations
highlight
synthetic
utility
this
protocol.
Organic Letters,
Год журнала:
2024,
Номер
26(31), С. 6736 - 6741
Опубликована: Июль 29, 2024
A
visible-light-induced
photoredox
three-component
carbocyclization
reaction
of
1,7-enynes
with
sulfoxonium
ylides
and
water
is
reported.
The
protocol
provides
a
facile
entry
to
structurally
valuable
highly
functionalized
cyclopenta[c]quinoline
scaffolds
in
chemoselective
stereoselective
manner.
Salient
features
this
method
include
redox-neutral
conditions,
no
requirement
base
or
other
additive,
good
functional-group
tolerance.
