Advanced Synthesis & Catalysis,
Journal Year:
2022,
Volume and Issue:
364(19), P. 3378 - 3383
Published: Aug. 18, 2022
Abstract
In
this
study,
we
developed
a
linear‐selective
allylation
reaction
of
aldehydes
using
simple
alkenes
as
starting
materials
by
quadruple
hybrid
catalyst
system.
The
proceeded
under
mild
conditions
such
room
temperature
visible
light
irradiation
and
was
applicable
to
asymmetric
reactions.
key
for
is
the
addition
Ni(BF
4
)
2
⋅
6H
O
previously
reported
ternary
system,
accelerating
allylic
transfer
process
from
branch
products
thermodynamically
stable
linear
increasing
Brønsted
acidity
thiophosphoric
imide
(TPI)
catalyst.
magnified
image
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(50), P. 23001 - 23009
Published: Dec. 8, 2022
A
new
regio-
and
stereoselective
reductive
coupling
of
alkynes
crotononitrile
has
been
developed
via
visible
light
organophotoredox
cobalt
dual
catalysis.
variety
enantioenriched
homoallylic
nitriles
bearing
a
stereodefined
trisubstituted
alkene
have
easily
synthesized
with
good
to
excellent
(up
>20:1
rr),
stereo-
(>20:1
E/Z),
enantioselectivity
98%
ee)
control
under
mild
conditions.
The
corresponding
nitrile
products
were
smoothly
converted
into
various
chiral
building
blocks.
Remarkably,
simple
organic
base
together
water
utilized
as
hydrogen
sources
in
this
photoinduced
reaction.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(24)
Published: April 12, 2023
Catalytic
metal
hydride
hydrogen
atom
transfer
(MHAT)
reactions
have
proven
to
be
a
powerful
method
for
alkene
functionalization.
This
work
reports
the
discovery
of
Co-porphines
as
highly
efficient
MHAT
catalysts
with
loading
only
0.01
mol
%
unprecedented
chemoselective
allene
functionalization
under
photoirradiation.
Moreover,
newly
developed
bimetallic
strategy
by
combination
photo
Co-MHAT
and
Ti
catalysis
enabled
successful
carbonyl
allylation
wide
range
amino,
oxy,
thio,
aryl,
alkyl-allenes
providing
expedient
access
valuable
β-functionalized
homoallylic
alcohols
in
over
100
examples
exceptional
regio-
diastereoselectivity.
Mechanism
studies
DFT
calculations
supported
that
selectively
transferring
atoms
from
cobalt
allenes
generating
allyl
radicals
is
key
step
catalytic
cycle.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(24), P. 5074 - 5081
Published: June 10, 2024
The
nickel/photoredox
dual
catalysis
system
is
an
efficient
conversion
platform
for
the
difunctionalization
of
unsaturated
hydrocarbons.
Herein,
we
disclose
first
nickel/photoredox-catalyzed
intramolecular
1,2-arylsulfonylation
allenes,
which
can
accurately
construct
a
C(sp2)–C(sp2)
bond
and
C(sp3)–S
bond.
reaction
exhibits
excellent
chemoselectivity
regioselectivity,
allowing
modular
conformations
diverse
series
3-sulfonylmethylbenzofuran
derivatives.
Control
experiments
showed
that
bipyridine
ligand
crucial
formation
stable
σ-alkyl
nickel
intermediate,
providing
possibility
sulfonyl
radical
insertion.
Meanwhile,
electrophilic
facilitates
further
oxidative
addition
intermediate
inhibits
with
allenes.
In
addition,
control
experiments,
cyclic
voltammetry
tests,
Stern–Volmer
density
functional
theory
calculations
afford
evidence
Ni(0)/Ni(I)/Ni(II)/Ni(III)
pathway
in
this
1,2-arylsulfonylation.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(1)
Published: Sept. 30, 2022
A
visible
light-induced
Co-catalyzed
highly
regio-
and
stereoselective
reductive
coupling
of
vinyl
azaarenes
alkynes
has
been
developed.
Notably,
Hünig's
base
together
with
simple
ethanol
successfully
applied
as
the
hydrogen
sources
instead
commonly
used
Hantzsch
esters
in
this
catalytic
photoredox
reaction.
This
approach
considerable
advantages
for
straightforward
synthesis
stereodefined
multiple
substituted
alkenes
bearing
an
azaarene
motif,
such
excellent
regioselectivity
(>20
:
1
>30
examples)
stereoselectivity
E/Z),
broad
substrate
scope
good
functional
group
compatibility
under
mild
reaction
conditions,
which
utilized
concise
natural
product
monomorine
I.
reasonable
pathway
involving
protolysis
cobaltacyclopentene
intermediate
proposed
based
on
mechanistic
studies.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 3, 2025
The
metal-catalyzed
hydrofunctionalization
reaction
of
allenes
is
an
efficient
approach
for
the
construction
new
allyl
compounds.
This
work
described
a
palladium-catalyzed/ligand-controlled
asymmetric
hydrosulfonylation
simple
alkylallenes
and
arylallenes
in
presence
Pd2dba3.
Using
Josiphos
or
Segphos
ligand,
could
render
corresponding
branched
chiral
allylsulfones
with
high
yields
enantioselectivities
up
to
90%
99%
ee,
respectively.
Angewandte Chemie International Edition,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 27, 2025
Abstract
Palladium‐catalyzed
cross
coupling
of
enolates—α‐arylation—is
an
established
method
for
chemical
synthesis.
A
major
challenge
in
the
field
is
control
stereochemistry
α‐carbon.
This
typically
due
to
facile
epimerization
under
basic
reaction
conditions
α‐arylation.
In
this
study,
alternative
approach
presented
that
involves
Pd/Cu‐catalyzed
arylboration
electron
deficient
alkenes.
The
products
are
generated
with
high
levels
diastereoselectivity
a
broad
range
substitution
patterns.
Enantioselective
variants
also
addition
product
derivatizations.
Angewandte Chemie,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 27, 2025
Abstract
Palladium‐catalyzed
cross
coupling
of
enolates—α‐arylation—is
an
established
method
for
chemical
synthesis.
A
major
challenge
in
the
field
is
control
stereochemistry
α‐carbon.
This
typically
due
to
facile
epimerization
under
basic
reaction
conditions
α‐arylation.
In
this
study,
alternative
approach
presented
that
involves
Pd/Cu‐catalyzed
arylboration
electron
deficient
alkenes.
The
products
are
generated
with
high
levels
diastereoselectivity
a
broad
range
substitution
patterns.
Enantioselective
variants
also
addition
product
derivatizations.
