Organometallics,
Journal Year:
2019,
Volume and Issue:
38(9), P. 2156 - 2166
Published: April 23, 2019
A
series
of
unsymmetrical
NNN′
ruthenium(II)
complexes
supported
by
a
tridentate
bipyridyl
imidazoline
ligand
with
variable
steric
hindrance
(2a–c;
R1
=
tBu,
iPr,
or
Bn)
and
electronic
effect
(2d–h;
R2
H,
CH3,
OCH3,
Br,
NO2)
were
prepared.
The
molecular
structures
ligands
1f
1g,
Ru
complex
2a
further
determined
X-ray
single-crystal
diffraction.
catalytic
activity
these
eight
for
α-alkylation
nitriles
alcohols
was
evaluated,
which
could
be
controlled
the
substituents
on
moiety.
2h
bearing
strong
electron-withdrawing
group
(R2
demonstrated
highest
activity,
alkylated
achieved
in
up
to
97%
yield.
Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
364(1), P. 47 - 52
Published: Oct. 11, 2021
Abstract
Herein,
we
describe
an
isolable,
air‐stable,
homogeneous,
nickel
catalyst
that
performs
dehydrogenative
cross‐coupling
reaction
between
secondary
and
primary
alcohols
to
result
α‐alkylated
ketone
products
selectively.
The
sequence
of
steps
involve
in
this
one‐pot
is
dehydrogenation
both
alcohols,
condensation
the
aldehyde,
hydrogenation
situ‐generated
α,β‐unsaturated
ketone.
Preliminary
mechanistic
investigation
hints
a
radical
mechanism
following
borrowing
hydrogen
reaction.
magnified
image
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
89(10), P. 6664 - 6676
Published: Jan. 3, 2023
Nickel(II)
complex
1
was
utilized
as
a
sustainable
catalyst
for
α-alkylation
of
arylacetonitriles
with
challenging
secondary
alcohols.
Arylacetonitriles
wide
range
functional
groups
were
tolerated,
and
various
cyclic
acyclic
alcohols
to
yield
large
number
α-alkylated
products.
The
plausible
mechanism
involves
the
base-promoted
activation
precatalyst
an
active
2
(dehydrochlorinated
product)
which
activates
O–H
C–H
bonds
alcohol
in
dehydrogenative
pathway.
Organometallics,
Journal Year:
2019,
Volume and Issue:
38(9), P. 2156 - 2166
Published: April 23, 2019
A
series
of
unsymmetrical
NNN′
ruthenium(II)
complexes
supported
by
a
tridentate
bipyridyl
imidazoline
ligand
with
variable
steric
hindrance
(2a–c;
R1
=
tBu,
iPr,
or
Bn)
and
electronic
effect
(2d–h;
R2
H,
CH3,
OCH3,
Br,
NO2)
were
prepared.
The
molecular
structures
ligands
1f
1g,
Ru
complex
2a
further
determined
X-ray
single-crystal
diffraction.
catalytic
activity
these
eight
for
α-alkylation
nitriles
alcohols
was
evaluated,
which
could
be
controlled
the
substituents
on
moiety.
2h
bearing
strong
electron-withdrawing
group
(R2
demonstrated
highest
activity,
alkylated
achieved
in
up
to
97%
yield.