Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(24), P. 4478 - 4482
Published: June 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.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
11(3), P. 895 - 915
Published: Dec. 20, 2023
Photoinduced
radical–polar
crossover
cyclization
(RPCC)
of
bifunctional
alkenes
is
high
synthetic
utility
to
produce
cyclic
products
with
precise
alkene
design.
This
review
summarizes
the
recent
representative
advances
in
field
RPC.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(8), P. 1719 - 1737
Published: Feb. 29, 2024
Abstract
Aryl
halides
are
one
of
the
most
important
chemical
feedstocks
in
pharmaceuticals
due
to
its
easy
accessibility,
inexpensiveness,
and
widely
utilized
as
aryl
radical
precursors
organic
synthetic
chemistry.
Conventionally,
stoichiometric
reagents
such
AIBN/n‐Bu
3
SnH
were
used
for
generation
from
halides,
suffered
requirement
toxic
initiators,
high
temperature
thus,
development
simple,
mild
strategies
highly
desirable.
Recently,
visible
light
mediated
received
considerable
attention,
allowing
under
reaction
conditions.
The
present
review
described
recent
breakthroughs
advancements
photocatalyst‐free
C−B/C/O/P/Se/S
bond
formation
halides.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(31)
Published: March 28, 2024
Abstract
Photoinduced
aryl
radical
generation
is
a
powerful
strategy
in
organic
synthesis
that
facilitates
the
formation
of
diverse
carbon‐carbon
and
carbon‐heteroatom
bonds.
The
synthetic
applications
photoinduced
complex
compounds,
including
natural
products,
physiologically
significant
molecules,
functional
materials,
have
received
immense
attention.
An
overview
current
developments
production
methods
their
uses
given
this
article.
A
generalized
idea
how
to
choose
reagents
approach
for
radicals
described,
along
with
techniques
associated
mechanistic
insights.
Overall,
article
offers
critical
assessment
results
as
well
selection
reaction
parameters
specific
context
cascades,
cross‐coupling
reactions,
functionalization,
selective
C−H
functionalization
substrates.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(18)
Published: Feb. 29, 2024
Abstract
The
rapid
assembly
of
valuable
cyclic
amine
architectures
in
a
single
step
from
simple
precursors
has
been
recognized
as
an
ideal
platform
term
efficiency
and
sustainability.
Although
vast
number
studies
regarding
synthesis
reported,
new
synthetic
disconnection
approaches
are
still
high
demand.
Herein,
we
report
catalytic
radical‐polar
crossover
cycloaddition
to
triggered
primary
sulfonamide
under
photoredox
condition.
This
newly
developed
disconnection,
comparable
established
approaches,
will
allow
construct
β,
β‐disubstituted
β‐monosubstituted
derivatives
efficiently.
study
highlights
the
unique
utility
bifunctional
reagent,
which
acts
radical
precursor
nucleophile.
open‐shell
methodology
demonstrates
broad
tolerance
various
functional
groups,
drug
natural
products
economically
sustainable
fashion.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(6)
Published: Jan. 8, 2024
Abstract
A
method
for
the
generation
of
tertiary
carbanions
via
a
deaminative
radical‐polar
crossover
is
reported
using
redox
active
imines
from
α‐tertiary
primary
amines.
variety
benzylic
amines
and
amino
esters
can
be
used
in
this
approach,
with
latter
engaging
novel
“aza‐Reformatsky”
reaction.
Electronic
trends
correlate
stability
resulting
carbanion
reaction
efficiency.
The
anions
trapped
different
electrophiles
including
aldehydes,
ketones,
imines,
Michael
acceptors,
H
2
O/D
O.
Selective
anion
formation
achieved
presence
another
equivalent
or
more
acidic
C−H
bond
both
an
inter‐
intramolecular
fashion.
Mechanistic
studies
suggest
intermediacy
discrete
intermediate.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(22), P. 4678 - 4683
Published: May 24, 2024
The
radical
1,4-functionalizations
of
1,3-enynes
have
emerged
as
a
powerful
strategy
for
the
synthesis
multisubstituted
allenes.
However,
phosphorus-centered
radical-initiated
transformations
remain
largely
elusive.
Herein,
visible-light
photoredox
catalytic
regioselective
hydrophosphinylation
with
diaryl
phosphine
oxides
phosphinoyl
precursors
has
been
realized.
This
protocol
features
mild
conditions,
wide
substrate
scope,
and
good
functional
group
tolerance,
producing
diverse
range
phosphinoyl-substituted
allenes
in
moderate
to
yields
high
atom
economy.
Detailed
mechanistic
experiments
revealed
radical-polar
crossover
process
reaction.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 8, 2025
Nozaki–Hiyama–Kishi
(NHK)
reactions
offer
a
mild
approach
for
the
formation
of
alcohol
motifs
through
radical-polar
crossover-based
pathways
from
various
radical
precursors.
However,
application
multicomponent
NHK-type
reactions,
which
allow
multiple
bonds
in
single
step,
has
been
largely
restricted
to
bulky
alkyl
precursors,
thus
limiting
their
expanded
utilization.
Herein,
we
disclose
general
three-component
reaction
enabled
by
delayed
crossover,
efficiently
tolerates
plethora
precursors
that
were
previously
unavailable.
This
method
enables
modular
assembly
versatile
homoallylic
alcohols
feedstock
chemicals
with
excellent
chemo-,
regio-,
diastereo-,
and
enantioselectivities
step.
Experimental
studies
density
functional
theory
(DFT)
calculations
reveal
kinetically
favored
an
allylchromium(III)
species
is
paramount
enforcing
crossover
over
direct
addition.
Finally,
straightforward
transformations
applications
products
demonstrated,
showcasing
synthetic
utility
this
method.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 10, 2025
Diastereoselective
synthesis
of
trans-3,4-difunctionalized
tetrahydroquinoline
and
chromane
derivatives
via
the
oxo-sulfonylation
1,7-enynes
is
demonstrated.
The
reaction
involves
a
three-component
oxidative
radical
polar
crossover
(ORPC)
approach
wherein
vinyl
carbocation
intermediate
undergoes
nucleophilic
substitution
to
afford
corresponding
keto
functional
group.
Deprotection
N-Ts
group,
gram-scale
synthesis,
other
synthetic
applications
were
illustrated.
Control
experiments
mechanistic
studies
show
that
water
acts
as
nucleophile
in
this
reaction.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Feb. 27, 2025
In
nature,
plants
convert
solar
energy
into
chemical
via
water
oxidation.
Inspired
by
natural
photosynthesis,
artificial
photosynthesis
has
been
gaining
increasing
interest
in
the
field
of
sustainability/green
science
and
technology
as
a
non-natural
thermodynamically
endergonic
(ΔG°
>
0,
uphill)
solar-energy-driven
reaction
that
uses
an
electron
donor
source
material.
Among
artificial-photosynthesis
processes,
inorganic-synthesis
reactions
oxidation,
including
splitting
CO2-to-fuel
conversion,
have
attracting
much
attention.
contrast,
synthesis
high-value
functionalized
organic
compounds
which
we
termed
directed
toward
(APOS),
remains
great
challenge.
Herein,
report
synthetically
pioneering
meaningful
strategy
APOS,
where
carbohydroxylation
C
=
double
bonds
is
accomplished
three-component
coupling
with
H2
evolution
using
dual
functions
semiconductor
photocatalysts,
i.e.,
silver-loaded
titanium
dioxide
(Ag/TiO2)
rhodium–chromium–cobalt-loaded
aluminum-doped
strontium
titanate
(RhCrCo/SrTiO3:Al).
Emulating
concept
long
focus
chemists
effort
to
harness
light
Here,
authors
present
photosynthetic
system
can
functionalize
styrenes
C–H
activation
splitting.
