Organic Letters,
Год журнала:
2023,
Номер
25(24), С. 4478 - 4482
Опубликована: Июнь 12, 2023
Multicomponent
reactions
represent
a
powerful
method
for
building
complex
molecules
from
structurally
simple
starting
materials.
Herein,
we
report
novel
three-component
radical–polar
crossover
reaction
involving
tandem
addition
of
two
different
olefins,
which
is
initiated
by
the
selective
fluorosulfonyl
radicals
to
alkyl
alkenes.
This
process
provides
facile
and
effective
access
multiple
functionalized
aliphatic
sulfonyl
fluoride
molecules.
Further
transformation
products
also
demonstrated.
Chemical Reviews,
Год журнала:
2021,
Номер
122(2), С. 2487 - 2649
Опубликована: Ноя. 9, 2021
Redox
processes
are
at
the
heart
of
synthetic
methods
that
rely
on
either
electrochemistry
or
photoredox
catalysis,
but
how
do
and
catalysis
compare?
Both
approaches
provide
access
to
high
energy
intermediates
(e.g.,
radicals)
enable
bond
formations
not
constrained
by
rules
ionic
2
electron
(e)
mechanisms.
Instead,
they
1e
mechanisms
capable
bypassing
electronic
steric
limitations
protecting
group
requirements,
thus
enabling
chemists
disconnect
molecules
in
new
different
ways.
However,
while
providing
similar
intermediates,
differ
several
physical
chemistry
principles.
Understanding
those
differences
can
be
key
designing
transformations
forging
disconnections.
This
review
aims
highlight
these
similarities
between
comparing
their
underlying
principles
describing
impact
electrochemical
photochemical
methods.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Фев. 4, 2025
Asymmetric
multicomponent
reactions
that
aim
to
control
multiple
chiral
centers
with
high
selectivity
in
a
single
step
remain
an
on-gonging
challenge.
The
realm
of
enantioselective
radical-polar
crossover
transformation
achieved
through
C-H
Functionalization
has
yet
be
fully
explored.
Herein,
we
present
successful
description
photoredox/Cr-catalyzed
three-component
(hetero)arylalkylation
1,3-dienes
functionalization.
A
diverse
array
homoallylic
alcohols
could
obtained
good
excellent
yields,
accompanied
by
outstanding
enantioselectivity.
asymmetric
build
two
simultaneously
and
demonstrates
broad
substrate
tolerance,
accommodating
various
drug-derived
aldehydes,
(hetero)aromatics,
1,3-diene
derivatives.
Preliminary
mechanistic
studies
indicate
the
involvement
radical
intermediate,
allylic
chromium
species
reacting
aliphatic
aromatic
aldehydes
Zimmerman–Traxler
transition
states
enabled
dual
photoredox
catalysis.
ongoing
Here,
authors
photoredox-
chromium-catalyzed
Molecules,
Год журнала:
2021,
Номер
26(22), С. 7051 - 7051
Опубликована: Ноя. 22, 2021
The
creation
of
new
bonds
via
C-F
bond
cleavage
readily
available
per-
or
oligofluorinated
compounds
has
received
growing
interest.
Using
such
a
strategy,
myriad
valuable
partially
fluorinated
products
can
be
prepared,
which
otherwise
are
difficult
to
make
by
the
conventional
formation
methods.
Visible
light
photoredox
catalysis
been
proven
as
an
important
and
powerful
tool
for
defluorinative
reactions
due
its
mild,
easy
handle,
environmentally
benign
characteristics.
Compared
classical
activation
that
proceeds
two-electron
processes,
radicals
key
intermediates
using
visible
catalysis,
providing
modes
bonds.
In
this
review,
summary
light-promoted
since
2018
was
presented.
contents
were
classified
fluorosubstrates,
including
polyfluorinated
arenes,
gem-difluoroalkenes,
trifluoromethyl
alkenes.
An
emphasis
is
placed
on
discussion
mechanisms
limitations
these
reactions.
Finally,
my
personal
perspective
future
development
rapidly
emerging
field
provided.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(11), С. 4952 - 4965
Опубликована: Март 11, 2022
We
report
a
general
protocol
for
the
convergent
synthesis
of
1,4-dicarbonyl
Z-alkenes
form
alkynes
using
α-diazo
sulfonium
triflate
and
water.
The
C═O,
C═C,
C–H
bonds
are
formed
under
mild
conditions
with
wide
range
functional
groups
tolerated.
reaction
exhibits
excellent
Z-selectivity
complete
regioselectivity.
resulting
can
smoothly
undergo
follow-up
conversion
to
variety
heteroaromatic
scaffolds.
Moreover,
also
provides
facile
access
corresponding
deuterated
heteroarenes
high
level
deuterium
incorporation
(90–97%
D-inc.)
by
directly
D2O,
thus
rendering
method
highly
valuable.
comprehensive
mechanistic
studies
indicate
that
free
carbyne
radical
intermediate
is
via
photocatalytic
single
electron
transfer
process,
KH2PO4
plays
crucial
role
in
significant
improvements
on
yield
selectivity
based
density-functional
theory
calculations,
providing
new
direction
coupling
reactions
diazo
compounds.
Chemical Science,
Год журнала:
2022,
Номер
13(24), С. 7256 - 7263
Опубликована: Янв. 1, 2022
Various
commercially
available
acyl
chlorides,
aldehydes,
and
alkanes
were
exploited
for
versatile
three-component
1,2-carboacylations
of
alkenes
to
forge
two
vicinal
C-C
bonds
through
the
cooperative
action
nickel
sodium
decatungstate
catalysis.
A
wealth
ketones
with
high
levels
structural
complexity
was
rapidly
obtained
via
direct
functionalization
C(sp2)/C(sp3)-H
in
a
modular
manner.
Furthermore,
regioselective
late-stage
modification
natural
products
showcased
practical
utility
strategy,
generally
featuring
resource
economy
ample
substrate
scope.
ACS Catalysis,
Год журнала:
2022,
Номер
12(6), С. 3279 - 3285
Опубликована: Фев. 25, 2022
A
visible
light-driven
photoredox-catalyzed
and
copper(II)-assisted
three-component
radical
addition/hydroxylation
reaction
of
alkenes,
sulfur
ylides,
water
is
reported.
This
process
shows
broad
substrate
scope
high
functional
group
tolerance,
with
respect
to
both
readily
available
ylides
providing
high-yielding
practical
access
valuable
γ-hydroxy
carbonyl
compounds.
Key
the
success
controlled
generation
α-carbonyl
carbon
radicals
from
via
sulfonium
salts
by
a
visible-light-driven
proton-coupled
electron
transfer
(PCET)
strategy
in
mixture
2,2,2-trifluoroethanol/CH2Cl2.
Addition
Cu(TFA)2·H2O
helps
accelerate
radical-cation
crossover
improve
efficiency.
Mechanistic
studies
suggest
that
hydroxy
moiety
products
stems
water.
study
also
builds
up
platform
for
further
investigation
into
synthetic
chemistry
ylides.
Chemical Science,
Год журнала:
2023,
Номер
14(22), С. 6045 - 6051
Опубликована: Янв. 1, 2023
A
photocatalytic
C-H
gem-difunctionalization
of
1,3-benzodioxoles
with
two
different
alkenes
for
the
synthesis
highly
functionalized
monofluorocyclohexenes
is
described.
Using
4CzIPN
as
photocatalyst,
direct
single
electron
oxidation
allows
their
defluorinative
coupling
α-trifluoromethyl
to
produce
gem-difluoroalkenes
in
a
redox-neutral
radical
polar
crossover
manifold.
The
bond
resultant
γ,γ-difluoroallylated
was
further
via
addition
electron-deficient
using
more
oxidizing
iridium
photocatalyst.
capture
situ
generated
carbanions
by
an
electrophilic
gem-difluoromethylene
carbon
and
consecutive
β-fluoride
elimination
afford
monofluorocyclohexenes.
synergistic
combination
multiple
termination
pathways
enables
rapid
incorporation
molecular
complexity
stitching
simple
readily
accessible
starting
materials
together.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(25)
Опубликована: Апрель 15, 2023
Abstract
In
this
study,
we
outline
a
general
method
for
photocatalyzed
difunctionalization
of
alkenes,
diene,
alkynes,
1,3‐enynes,
and
[1.1.1]propellane
using
dithiosulfonate
reagents
(ArSO
2
‐SSR)
with
improved
atom
economy.
Both
“ArSO
‐”
“‐SSR”
on
the
are
transferred
under
mild
conditions
broad
substrate
scope,
high
stereoselectivity,
complete
regioselectivity.
Significantly,
resulting
dithiosulfonylated
styrene
is
practical
nucleophilic
disulfuration
reagent,
reacting
variety
electrophiles
efficiently.
reactions
can
be
conducted
gram
scale,
rendering
approach
highly
valuable.
