Abstract
Transition‐metal‐catalyzed
α‐alkylation
of
nitriles
with
alcohols
is
an
environmentally
benign
reaction,
and
the
development
simple
efficient
catalysts
for
this
transformation
a
growing
area
research.
In
study,
we
report
serial
bidentate
N
‐heterocyclic
carbene
(NHC)
ruthenium
complexes
different
extra
donors
alcohols.
Through
adjusting
backbone
NHC
ligands,
catalytic
activities
these
could
be
controlled.
The
complex
(
Ru3
)
bearing
amine
donor
benzimidazolium
exhibited
highest
activity.
A
large
variety
α‐alkylated
were
obtained
in
30%–88%
yields,
by
using
1
mol%
amount
Cs
2
CO
3
(20
mol%).
Detailed
control
experiments
deuterium‐labeling
suggested
that
reaction
proceeds
via
borrowing
hydrogen
pathway.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
89(10), С. 6664 - 6676
Опубликована: Янв. 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.
Inorganic Chemistry,
Год журнала:
2024,
Номер
63(25), С. 11821 - 11831
Опубликована: Июнь 7, 2024
A
series
of
ruthenium
complexes
(Ru1–Ru4)
bearing
new
NNN-pincer
ligands
were
synthesized
in
58–78%
yields.
All
the
are
air
and
moisture
stable
characterized
by
IR,
NMR,
high-resolution
mass
spectra
(HRMS).
In
addition,
structures
Ru1–Ru3
confirmed
X-ray
crystallographic
analysis.
These
Ru(II)
exhibited
high
catalytic
efficiency
broad
functional
group
tolerance
N-methylation
reaction
amines
using
CH3OH
as
both
C1
source
solvent.
Experimental
results
indicated
that
electronic
effect
substituents
on
considerably
affects
reactivity
which
Ru3
an
electron-donating
OMe
showed
highest
activity.
Deuterium
labeling
control
experiments
suggested
dehydrogenation
methanol
to
generate
hydride
species
was
rate-determining
step
reaction.
Furthermore,
this
protocol
also
provided
a
ready
approach
versatile
trideuterated
N-methylamines
under
mild
conditions
CD3OD
deuterated
methylating
agent.
Organic Letters,
Год журнала:
2021,
Номер
23(13), С. 5028 - 5032
Опубликована: Июнь 18, 2021
The
first
switchable
α-olefination
and
α-alkylation
of
nitriles
with
primary
alcohols
catalyzed
by
a
well-defined
base
transition-metal
Co
complex
was
presented.
A
broad
variety
are
selectively
efficiently
converted
to
the
corresponding
products
this
method.
It
is
noteworthy
that
transformation
environmentally
benign
atom
efficient
H2
H2O
being
sole
byproducts.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(38)
Опубликована: Июль 22, 2022
A
facile
benzylic
alkylation
of
indenes
and
other
arenes
was
developed
from
readily
available
primary
secondary
alcohols
using
our
newly
investigated
CCC
pincer
IrIII
catalyst
(SNIr-H).
Excellent
regioselectivity
yield
(89
%)
the
C3-alkylated
were
obtained.
Additionally,
challenging
sp2
C-alkylation
accomplished.
This
method
could
be
utilized
for
synthesis
analogs
a
histamine
H1
receptor
antagonist
functional
material
template
molecule,
indeno[2,1-a]indene.
hemilabile
-dihydride
intermediate
proposed
based
on
control
experiments
previous
density
theory
(DFT)
calculations
borrowing
hydrogen
mechanism
is
key
to
success
this
in
reduction
unactivated
multi-substituted
olefin
intermediates.
Chemical Communications,
Год журнала:
2022,
Номер
58(71), С. 9930 - 9933
Опубликована: Янв. 1, 2022
A
highly
chemoselective
transfer
hydrogenation
of
α,β-unsaturated
ketones
was
achieved
with
the
Cp*Ir/bipy-diol
catalytic
system
using
methanol
as
a
hydrogen
surrogate
at
room
temperature.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(11), С. 7162 - 7171
Опубликована: Май 10, 2023
Herein,
we
have
demonstrated
a
simple
nickel-catalyzed
C-3-selective
alkylation
of
2-oxindoles
using
wide
variety
secondary
alkyl
alcohols.
As
special
highlight,
functionalization
the
cholesterol
derivative
was
reported.
Control
experiments,
initial
mechanistic
studies,
and
deuterium-labeling
experiments
were
performed
for
process.
Abstract
Cross‐coupling
of
nitriles
and
alcohols
offers
an
environmentally
friendly
atom‐economical
method
for
the
synthesis
various
valuable
compounds.
These
compounds
include
α
‐alkylated
‐olefinated
nitriles,
primary
amines,
imines,
N
‐alkylation
amides,
‐heterocycles,
δ
‐hydroxynitriles,
olefins,
etc
.
Herein,
we
have
reviewed
recent
developments
(from
2013–date)
transition‐metal‐catalyzed
cross‐coupling
alcohols.
A
number
transition
metal
complexes
such
as
noble
metals
Ru
Ir,
well
base
Mn,
Fe,
Co,
Ni
are
presented.
Moreover,
different
product
types,
reaction
conditions
mechanisms
discussed
to
understand
catalyst
development.
The Journal of Organic Chemistry,
Год журнала:
2020,
Номер
85(23), С. 14980 - 14988
Опубликована: Ноя. 2, 2020
The
α-alkylation
of
nitriles
with
primary
alcohols
to
selectively
synthesize
by
a
well-defined
molecular
homogeneous
cobalt
catalyst
is
presented.
Thirty-two
examples
up
95%
yield
are
reported.
Remarkably,
this
transformation
environmentally
friendly
and
atom
economical
water
as
the
only
byproduct.
Chemical Science,
Год журнала:
2021,
Номер
12(42), С. 14217 - 14223
Опубликована: Янв. 1, 2021
A
well-defined,
bench-stable
nickel
catalyst
is
presented
here,
that
can
facilitate
double
alkylation
of
a
methyl
ketone
to
realize
wide
variety
cycloalkanes.
The
performance
the
depends
on
ligand
redox
process
comprising
an
azo-hydrazo
couple.
source
bis
electrophile
in
this
1,n-diol,
so
(n+1)-membered
cycloalkanes
be
furnished
stereoselective
manner.
reaction
follows
cascade
dehydrogenation/hydrogenation
reactions
and
adopts
borrowing
hydrogen
(BH)
method.
thorough
mechanistic
analysis
including
interception
key
radical
intermediates
DFT
calculations
supports
radical-mediated
dehydrogenation
hydrogenation
reactions,
which
quite
rare
BH
chemistry.
In
particular,
radical-promoted
distinctly
different
from
conventional
hydrogenations
involving
metal
hydride
complementary
ubiquitous
two-electron
driven
reactions.
