Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(22), P. 8816 - 8821
Published: Nov. 2, 2021
Conjugated
dienes
are
versatile
building
blocks
and
prevalent
substructures
in
synthetic
chemistry.
Herein,
we
report
a
method
for
the
stereoselective
hydroalkenylation
of
alkynes,
utilizing
readily
available
enol
triflates.
We
leveraged
an
situ-generated
geometrically
pure
vinyl-Cu(I)
species
to
form
Z,Z-
or
Z,E-1,3-dienes
excellent
stereoselectivity
yield.
This
approach
allowed
synthesis
highly
substituted
Z-dienes,
including
pentasubstituted
1,3-dienes,
which
difficult
prepare
by
existing
approaches.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(24), P. 17479 - 17646
Published: Oct. 14, 2022
Alkenes
and
their
derivatives
are
featured
widely
in
a
variety
of
natural
products,
pharmaceuticals,
advanced
materials.
Significant
efforts
have
been
made
toward
the
development
new
practical
methods
to
access
this
important
class
compounds
by
selectively
activating
alkenyl
C(sp2)–H
bonds
recent
years.
In
comprehensive
review,
we
describe
state-of-the-art
strategies
for
direct
functionalization
sp2
C–H
C–F
until
June
2022.
Moreover,
metal-free,
photoredox,
electrochemical
also
covered.
For
clarity,
review
has
divided
into
two
parts;
first
part
focuses
on
currently
available
using
different
alkene
as
starting
materials,
second
describes
bond
easily
accessible
gem-difluoroalkenes
material.
This
includes
scope,
limitations,
mechanistic
studies,
stereoselective
control
(using
directing
groups
well
metal-migration
strategies),
applications
complex
molecule
synthesis
where
appropriate.
Overall,
aims
document
considerable
advancements,
current
status,
emerging
work
critically
summarizing
contributions
researchers
working
fascinating
area
is
expected
stimulate
novel,
innovative,
broadly
applicable
functionalizations
coming
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(42), P. 22956 - 22962
Published: Aug. 18, 2021
Abstract
Kharasch–Sosnovsky
reaction
is
one
of
the
most
powerful
methods
for
allylic
oxidation
alkenes.
However,
inherent
radical
mechanism
and
use
peroxides
as
both
oxidants
oxygen
nucleophiles
render
dearth
universal
catalytic
systems
highly
enantioselective
variants
limited
scope.
Herein,
an
alternative
to
asymmetric
that
utilized
a
chiral
copper
catalyst
purple‐LED
irradiation
enable
three‐component
coupling
1,3‐dienes,
oxime
esters,
carboxylic
acids
reported.
This
protocol
features
mild
conditions,
remarkable
scope
functional
group
tolerance
evidenced
by
>80
examples
utility
in
late‐stage
modification
pharmaceuticals
natural
products.
Detailed
mechanistic
studies
provide
evidences
radical‐based
pathway.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Jan. 4, 2023
Precise
stereocontrol
of
functionalized
alkenes
represents
a
long-standing
research
topic
in
organic
synthesis.
Nevertheless,
the
development
catalytic,
easily
tunable
synthetic
approach
for
stereodivergent
synthesis
both
E-selective
and
even
more
challenging
Z-selective
highly
substituted
1,3-dienes
from
common
substrates
remains
underexploited.
Here,
we
report
photoredox
nickel
dual
catalytic
strategy
sulfonylalkenylation
terminal
alkynes
with
vinyl
triflates
sodium
sulfinates
under
mild
conditions.
With
judicious
choice
simple
catalyst
ligand,
this
method
enables
efficient
divergent
access
to
Z-
E-sulfonyl-1,3-dienes
same
set
starting
materials.
This
features
broad
substrate
scope,
good
functional
compatibility,
excellent
chemo-,
regio-,
stereoselectivity.
Experimental
DFT
mechanistic
studies
offer
insights
into
observed
stereoselectivity
controlled
by
ligands.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(20)
Published: March 4, 2024
Abstract
Dienes
have
been
of
great
interest
to
synthetic
chemists
as
valuable
substrates
due
their
abundance
and
ease
synthesis.
Their
unique
stereoelectronic
properties
enable
broad
reactivity
with
a
wide
range
transition
metals
construct
molecular
complexity
facilitating
synthesis
biologically
active
compounds.
In
addition,
structural
diene
variation
can
result
in
substrate‐controlled
reactions,
providing
mechanistic
insights
into
selectivity
patterns.
The
last
decade
has
seen
wealth
new
methodologies
involving
through
the
power
metal
catalysis.
This
review
summarizes
recent
advances
remaining
opportunities
for
metal‐catalyzed
transformations
dienes.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(24), P. 15638 - 15647
Published: Dec. 6, 2022
Ni-catalyzed
enantioselective
hydrofunctionalizations
of
conjugated
dienes
are
particularly
demanding
reactions
to
devise
because
they
require
not
only
addressing
the
inherent
challenges
associated
with
development
an
transformation
but
also
overcoming
all
other
aspects
selective
catalysis
(chemoselectivity,
regioselectivity,
diastereoselectivity,
etc.).
However,
value-added
nature
chiral
allylic
and
homoallylic
derivatives
obtained
by
these
methods,
lack
efficient
alternatives,
use
earth-abundant
first-row
transition
metal
have
led
renewed
interest
over
past
decade.
In
this
Perspective,
we
give
overview
developments
in
field,
from
original
findings
(often
dating
back
last
century)
most
recent
contributions.
Emphasis
is
placed
on
hydrofunctionalization
agent
(C(sp),
C(sp2),
C(sp3),
N,
P,
or
O).
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(12), P. 8508 - 8519
Published: Feb. 21, 2024
Tricomponent
cobalt(salen)-catalyzed
carbofunctionalization
of
unsaturated
substrates
by
radical-polar
crossover
has
the
potential
to
streamline
access
broad
classes
heteroatom-functionalized
synthetic
targets,
yet
reaction
platform
remained
elusive,
despite
well-developed
analogous
hydrofunctionalizations
mediated
high-valent
alkylcobalt
intermediates.
We
report
herein
development
a
cobalt(salen)
catalytic
system
that
enables
carbofunctionalization.
The
entails
tricomponent
decarboxylative
1,4-carboamination
dienes
and
provides
direct
route
aromatic
allylic
amines
obviating
preformed
allylation
reagents
protection
oxidation-sensitive
amines.
merges
acridine
photocatalysis
with
regioselective
1,4-carbofunctionalization
facilitates
radical
polar
phases
coupling
process,
revealing
critical
roles
reactants,
as
well
ligand
effects
nature
formal
species
on
chemo-
regioselectivity.
iScience,
Journal Year:
2024,
Volume and Issue:
27(3), P. 109223 - 109223
Published: Feb. 15, 2024
SummaryIn
recent
years,
significant
advancements
have
been
made
in
the
synthesis
and
application
of
1,3-dienes.
This
specific
structural
motif
has
garnered
attention
from
researchers
materials
science
biology
due
to
its
unique
aggregation-induced
emission
(AIE)
properties
extensive
conjugation
systems.
The
luminescent
characteristics
these
compounds
are
notably
influenced
by
geometry
two
double
bonds.
Therefore,
it
is
essential
consolidate
stereoselective
synthetic
strategies
for
comprehensive
review
seeks
elucidate
diverse
techniques
employed
attain
stereo-control
1,3-diene-based
AIE
luminogens
(AIEgens).
Particular
emphasis
placed
on
comprehending
determinants
stereoselectivity
exploring
array
substrates
amenable
methods.
Furthermore,
underscores
exhibited
their
utility
organic
light-emitting
diodes
(OLEDs),
stimuli-responsive
materials,
sensors,
bioimaging,
photodynamic
therapy
(PDT).Graphical
abstract
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(32), P. 18115 - 18125
Published: Aug. 1, 2023
We
report
the
first
catalyst-controlled
regiodivergent
method
that
enables
synthesis
of
structurally
diverse
1,2,3,4-tetrasubstituted
conjugated
dienes
with
excellent
regio-
and
stereochemical
outcomes
from
same
set
readily
available
propargyl
esters
diaryliodonium
salts.
In
this
diene
chemistry,
in
situ
generated,
highly
electrophilic
aryl-CuIII
complex
serves
not
only
as
a
π-Lewis
acid
catalyst
for
alkyne
activation/acyloxy
migration
but
also
an
aryl
electrophile
equivalent.
The
competitive
arylative
1,2-
1,3-acyloxy
patterns
are
exquisitely
dictated
by
Cu
Au/Cu
relay
catalyses,
respectively,
providing
modular
attractive
approach
to
traditionally
inaccessible
tetrasubstituted
1,3-dienes
manner.
Finally,
synthetic
utility
is
demonstrated
further
derivatization
into
array
useful
compounds.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(13), P. 7970 - 7977
Published: June 16, 2021
A
Ru-catalyzed
conjugative
isomerization
of
remote
alkenes
that
affords
branched
1,3-dienes
is
described.
These
kinetic
products
are
obtained
in
high
yields,
good
levels
regiocontrol,
and
stereoselectivity.
broad
range
functional
groups
heterocycles
compatible
with
the
mild
reaction
conditions,
sustained
over
long
distances.
Control
experiments
support
a
metal-hydride
mechanism
consisting
iterative
migratory
insertions/β-H
eliminations,
which
initiated
preferentially
at
terminal
olefinic
site.
Two
one-pot
multimetallic
selective
catalytic
sequences
using
[Ru/Cu]
[Ru/Rh]
combinations
have
been
developed
to
illustrate
synthetic
potential
process.
