European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(30)
Published: March 22, 2024
Abstract
Allenes
represent
a
distinctive
class
of
organic
molecules
characterized
by
their
unique
physical
and
chemical
properties.
Among
them,
chiral
allenes
play
significant
role
in
modern
chemistry.
They
not
only
serve
as
pivotal
frameworks
for
natural
products
drug
but
also
are
essential
building
blocks
synthesis.
Over
the
years,
numerous
remarkable
efficient
methods
have
been
developed
synthesis
allenes.
Notably,
catalytic
using
transition
metals
conjunction
with
ligands
has
garnered
considerable
attention.
This
review
paper
aims
to
provide
an
overview
recent
advancements
through
asymmetric
1,4‐difunctionalization
1,3‐enynes,
which
two
distinct
strategies
including
non‐radical
radical
processes
highlighted.
Chinese Journal of Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 25, 2025
Comprehensive
Summary
Vicinal
all‐carbon
quaternary
stereocenters
are
widely
present
in
natural
products
and
bioactive
molecules.
However,
the
construction
of
such
motif
one
step
from
readily
available
starting
materials
remains
a
significant
challenge.
Herein,
we
report
phosphine‐catalyzed
divergent
γ,γ‐
ε,γ‐umpolung
domino
addition
bisoxindoles
with
allenoates.
This
method
serves
as
practical
tool
for
concise
synthesis
series
bisoxindole
derivatives
bearing
sterically
hindered
vicinal
under
mild
reaction
conditions.
The
applicability
this
novel
was
demonstrated
gram‐scale
three
known
advanced
intermediates
total
syntheses
calycanthine,
chimonanthine
folicanthine.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(18), P. 4488 - 4515
Published: Jan. 1, 2023
This
review
highlights
the
recent
advances
in
radical
acylated
difunctionalization
of
unsaturated
carbon–carbon
bonds
and
focuses
on
mechanistic
insights
these
transformations.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(2), P. 536 - 541
Published: Jan. 5, 2024
In
the
presence
of
visible
light
irradiation,
organophoto/nickel
dual
catalysts,
and
mild
base
K2HPO4,
1,3-enynes
react
with
silanecarboxylic
acids
to
give
corresponding
α-silylallenes
high
selectivity.
this
uniquely
decarboxylative
hydrosilylation
1,3-enynes,
a
silyl
radical
process
is
involved
diverse
electron-rich
-poor
substrates
proceed
smoothly
in
moderate
excellent
yields.
This
transformation
particularly
synthetically
worthwhile
when
using
MeOD
as
solvent,
which
furnishes
new
access
α-silyldeuteroallenes.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(11), P. 7419 - 7430
Published: March 6, 2024
The
first
earth-abundant
transition
metal
Ni-catalyzed
highly
regio-
and
enantioselective
semihydrogenation
of
racemic
tetrasubstituted
allenes
via
a
kinetic
resolution
process
as
challenging
task
was
well
established.
This
protocol
furnishes
expedient
access
to
diversity
structurally
important
enantioenriched
chiral
allylic
molecules
with
high
regio-,
enantio-,
Z/E-selectivity.
Remarkably,
this
proceeded
one
carbon–carbon
double
bond
allenes,
which
regioselective
complementary
the
Rh-catalyzed
asymmetric
version.
Deuterium
labeling
experiments
density
functional
theory
(DFT)
calculations
were
carried
out
reveal
reasonable
reaction
mechanism
explain
regio-/stereoselectivity.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(17), P. 10192 - 10280
Published: Aug. 8, 2024
Radical
C–H
functionalization
represents
a
useful
means
of
streamlining
synthetic
routes
by
avoiding
substrate
preactivation
and
allowing
access
to
target
molecules
in
fewer
steps.
The
first-row
transition
metals
(Ti,
V,
Cr,
Mn,
Fe,
Co,
Ni,
Cu)
are
Earth-abundant
can
be
employed
regulate
radical
functionalization.
use
such
is
desirable
because
the
diverse
interaction
modes
between
metal
complexes
species
including
addition
center,
ligand
complexes,
substitution
single-electron
transfer
radicals
hydrogen
atom
noncovalent
complexes.
Such
interactions
could
improve
reactivity,
diversity,
selectivity
transformations
allow
for
more
challenging
reactions.
This
review
examines
achievements
this
promising
area
over
past
decade,
with
focus
on
state-of-the-art
while
also
discussing
existing
limitations
enormous
potential
high-value
regulated
these
metals.
aim
provide
reader
detailed
account
strategies
mechanisms
associated
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.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(15), P. 2955 - 2959
Published: April 3, 2024
An
Eosin
Y-catalyzed
visible
light-promoted
1,4-peroxidation–sulfonylation
of
enynones
was
achieved
to
give
tetrasubstituted
allenes.
The
photoredox
catalysis
Y
allowed
the
concomitant
formation
peroxy
and
sulfonyl
radicals,
where
preferential
radical
addition
alkene
moiety
resulted
in
subsequent
α-keto
radical–sulfonyl
cross
couplings.
developed
demonstrates
a
regioselective
1,4-diradical
strategy,
opening
up
new
possibility
diradical
functionalization
conjugate
systems.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(11), P. 2773 - 2781
Published: Jan. 1, 2023
A
regio-
and
enantioselective
radical
three-component
coupling
of
1,3-enynes,
oxime
esters,
carboxylic
acids
through
photoinduced
copper
catalysis
is
reported.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(3), P. 2142 - 2148
Published: Jan. 25, 2023
Allenol
has
been
identified
as
a
versatile
building
block
for
organic
synthesis,
and
numerous
efforts
have
made
to
synthesize
apply
allenol.
However,
limited
obtain
trifluoromethyl-substituted
Here,
by
using
readily
available
1,3-enyne
the
starting
material,
copper-catalyzed
trifluoromethylbenzoxylation
process
was
developed
efficient
synthesis
of
allenols
Togni-II
reagent
reaction
partner.
Triple
roles
reagent,
including
source
trifluoromethyl
group,
hydroxyl
oxidant,
were
elucidated
in
this
transformation.
Moreover,
late-stage
diversification
performed,
which
revealed
application
potential
preparation
various
compounds.
