Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(45)
Published: Oct. 2, 2023
Abstract
Light
olefins
are
abundantly
manufactured
in
the
petroleum
industry
and
thus
represent
ideal
starting
materials
for
modern
chemical
synthesis.
Selective
divergent
transformations
of
feedstock
light
to
value‐added
chemicals
highly
sought‐after
but
remain
challenging.
Herein
we
report
an
exceptionally
regioselective
carbonickelation
alkenes
followed
by
situ
trapping
with
three
types
nucleophiles,
namely
a
reductant,
base,
or
Grignard
reagent.
This
protocol
enables
efficient
1,2‐hydrofunctionalization,
dicarbofunctionalization,
branched‐selective
Heck‐type
cross‐coupling
aryl
alkenyl
reagents
streamline
access
diverse
alkyl
arenes
complex
alkenes.
Harnessing
bulky
N
‐heterocyclic
carbene
ligands
acenaphthyl
backbones
nickel
catalysts
is
crucial
attain
high
reactivity
selectivity.
strategy
provides
rare,
modular,
platform
upgrading
expected
find
broad
applications
medicinal
chemistry
industrial
processes.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Feb. 6, 2025
Compared
with
rare-earth
(RE)…heteroatom
interaction,
RE…π
frequently
used
in
facilitating
regio-
and
stereoselectivity
of
olefin
polymerizations,
is
seldomly
to
trigger
catalytic
C
-
H
functionalization.
Here,
we
describe
a
direct
anti-Markovnikov
hydroallylation
reaction
styrene
derivatives
1-aryl-2-alkyl
alkenes
α-alkenes
by
use
interaction.
This
protocol
provides
straightforward
atom-efficient
route
for
the
synthesis
valuable
chain
elongated
internal
(65
examples,
up
99%
yield,
>
19:1
E/Z
ratio).
The
proceeds
via
an
allylic
Csp3‒H
activation
pathway
initiated
site-selective
deprotonation
assistance
cationic
imidazolin-2-iminato
scandium
alkyl
species
followed
alkene
insertion
into
resulting
scandium-allyl
bond.
A
amount
Lewis
base
additives,
such
as
amine
tetrahydrofuran
(THF)
show
significant
effects
on
reactivity
selectivity.
mechanism
elucidated
experimental
studies
theoretical
calculations.
Advanced Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 18, 2024
Abstract
For
traditional
metal
complexes,
intricate
chemistry
is
required
to
acquire
appropriate
ligands
for
controlling
the
electron
and
steric
hindrance
of
active
centers.
Comparatively,
preparation
single‐atom
catalysts
much
easier
with
more
straightforward
effective
accesses
arrangement
control
The
presence
coordination
atoms
or
neighboring
functional
on
supports'
surface
ensures
stability
single‐atoms
their
interactions
individual
substantially
regulate
performance
Therefore,
collaborative
interaction
between
surrounding
environment
enhances
initiation
reaction
substrates
formation
transformation
crucial
intermediate
compounds,
which
imparts
significant
catalytic
efficacy,
rendering
them
a
valuable
framework
investigating
correlation
structure
activity,
as
well
mechanism
in
organic
reactions.
Herein,
comprehensive
overviews
both
homogeneous
complexes
reactions
are
provided.
Additionally,
reflective
conjectures
about
advancement
synthesis
also
proposed
present
reference
later
development.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(16)
Published: Feb. 13, 2024
Abstract
We
report
a
highly
enantioselective
intermolecular
C−H
bond
silylation
catalyzed
by
phosphoramidite‐ligated
iridium
catalyst.
Under
reagent‐controlled
protocols,
propargylsilanes
resulting
from
C(sp
3
)−H
functionalization,
as
well
the
regioisomeric
and
synthetically
versatile
allenylsilanes,
could
be
obtained
with
excellent
levels
of
enantioselectivity
good
to
control
propargyl/allenyl
selectivity.
In
case
unsymmetrical
dialkyl
acetylenes,
selectivity
for
functionalization
at
less‐hindered
site
was
also
observed.
A
variety
electrophilic
silyl
sources
(R
SiOTf
R
SiNTf
2
),
either
commercial
or
in
situ
‐
generated,
were
used
reagents,
broad
range
simple
functionalized
alkynes,
including
aryl
alkyl
1,3‐enynes,
drug
derivatives
successfully
employed
substrates.
Detailed
mechanistic
experiments
DFT
calculations
suggest
that
an
η
‐propargyl/allenyl
Ir
intermediate
is
generated
upon
π‐complexation‐assisted
deprotonation
undergoes
outer‐sphere
attack
silylating
reagent
give
propargylic
silanes,
latter
step
identified
enantiodetermining
step.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(23), P. 8850 - 8857
Published: Jan. 1, 2024
Cyclopentadienyliron(
ii
)
dicarbonyl
complexes
capable
of
coordinating
to
and
enhancing
the
acidity
a
range
unsaturated
substrates
have
emerged
as
new
class
base-metal
derived
catalysts
for
C–H
functionalization.
A
novel
palladium-catalyzed
allylic
C-H
alkylation
of
terminal
olefins
with
3-carboxamide
oxindoles
is
described.
variety
new
3-carboxamide-3-allylation
an
all-carbon
quaternary
center
were
obtained
in
moderate
to
good
yields
(up
99%).
In
addition,
the
asymmetric
version
this
reaction
was
also
explored,
providing
enantioselectivity.
Chemistry - An Asian Journal,
Journal Year:
2023,
Volume and Issue:
19(1)
Published: Dec. 5, 2023
Abstract
Iron‐catalyzed
C−H
activation
has
recently
emerged
as
an
increasingly
powerful
synthetic
method
for
the
step‐
and
atom‐
economical
direct
functionalizations
of
otherwise
inert
bonds.
Iron's
low‐cost
toxicity
along
with
its
catalytic
versatility
have
encouraged
scientific
community
to
elect
this
metal
development
new
methodologies.
Within
review,
we
aim
present
a
collection
most
recent
examples
iron‐catalyzed
particular
emphasis
on
modern
strategies
mechanistic
aspects.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(9), P. 1420 - 1424
Published: Feb. 27, 2023
The
iron-catalyzed
coupling
of
alkenes
and
enones
through
allylic
C(sp3)–H
functionalization
is
reported.
This
redox-neutral
process
employs
a
cyclopentadienyliron(II)
dicarbonyl
catalyst
simple
alkene
substrates
to
generate
catalytic
allyliron
intermediates
for
1,4-addition
chalcones
other
conjugated
enones.
use
2,4,6-collidine
as
the
base
combination
triisopropylsilyl
triflate
LiNTf2
Lewis
acids
was
found
facilitate
this
transformation
under
mild,
functional
group-tolerant
conditions.
Both
electronically
unactivated
well
allylbenzene
derivatives
could
be
employed
pronucleophilic
partners,
range
bearing
varied
substituents.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(45), P. 8178 - 8182
Published: Nov. 7, 2023
CO2-assisted
and
Ni-catalyzed
direct
reductive
allylation
of
aldehydes
utilizing
allylic
alcohols
as
precursor
has
been
reported.
Various
homoallyl
could
be
synthesized
in
excellent
yield
with
enhanced
regioselectivity
stereoselectivity
for
alkyl-
aryl-substituted
under
mild
conditions.
For
different
substrates,
proper
collocation
the
catalytic
ligand
is
crucial.
Preliminary
mechanistic
studies
supported
reaction
pathway
through
a
sequential
allyl
hydrocarbonate
formation/allylnickelation/coordination
insertion
process
by
Ni(I)/Ni(III)
cycle,
which
proven
cyclic
voltammetry
analysis.
