The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(8), С. 5250 - 5265
Опубликована: Март 30, 2024
The
synthesis,
characterization,
and
catalytic
application
of
a
new
phosphine-free,
well-defined,
water-soluble,
air-stable
Mn(II)-catalyst
[Mn(L)(H2O)2Cl](Cl)
([1]Cl)
featuring
1,10-phenanthroline
based
tridentate
pincer
ligand,
2-(1H-pyrazol-1-yl)-1,10-phenanthroline
(L),
in
dehydrogenative
functionalization
alcohols
to
various
N-heterocycles
such
as
quinazolin-4(3H)-ones,
quinolines,
quinoxalines
are
reported
here.
A
wide
array
multisubstituted
quinazolin-4(3H)-ones
were
prepared
water
under
air
following
two
pathways
via
the
coupling
with
2-aminobenzamides
2-aminobenzonitriles,
respectively.
2-Aminobenzyl
alcohol
ketones
bearing
active
methylene
group
used
partners
for
synthesizing
quinoline
derivatives,
quinoxaline
derivatives
by
vicinal
diols
1,2-diamines.
In
all
cases,
reaction
proceeded
smoothly
using
our
[1]Cl
air,
affording
desired
satisfactory
yields
starting
from
cheap
readily
accessible
precursors.
Gram-scale
synthesis
compounds
indicates
industrial
relevance
synthetic
strategy.
Control
experiments
performed
understand
unveil
plausible
mechanism.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(11), С. 4386 - 4464
Опубликована: Янв. 1, 2022
The
emerging
field
of
organometallic
catalysis
has
shifted
towards
research
on
Earth-abundant
transition
metals
due
to
their
ready
availability,
economic
advantage,
and
novel
properties.
In
this
case,
manganese,
the
third
most
abundant
transition-metal
in
Earth's
crust,
emerged
as
one
leading
competitors.
Accordingly,
a
large
number
molecularly-defined
Mn-complexes
been
synthesized
employed
for
hydrogenation,
dehydrogenation,
hydroelementation
reactions.
regard,
catalyst
design
is
based
three
pillars,
namely,
metal-ligand
bifunctionality,
ligand
hemilability,
redox
activity.
Indeed,
developed
catalysts
not
only
differ
chelating
atoms
they
possess
but
also
working
principles,
thereby
different
turnover
numbers
product
molecules.
Hence,
critical
assessment
molecularly
defined
manganese
terms
atoms,
reaction
conditions,
mechanistic
pathway,
significant.
Herein,
we
analyze
complexes
catalytic
activity,
versatility
allow
multiple
transformations
routes
convert
substrates
target
This
article
will
be
helpful
get
significant
insight
into
design,
aiding
design.
Coordination Chemistry Reviews,
Год журнала:
2021,
Номер
443, С. 213967 - 213967
Опубликована: Май 24, 2021
Catalytic
dehydrogenation
of
alcohols
represents
an
attractive
approach
for
future
applications
as
hydrogen
storage
systems
and
clean
synthesis
fine
chemicals.
Herein,
overview
recent
progress
in
homogeneously
catalyzed
acceptorless
alcohol
is
presented.
In
Nature,
efficiently
by
multiple
metalloenzymes
where
a
non-noble
metal–ligand
interplay
key
to
activate
transform
substrate.
We
highlight
the
introduction
multifunctional
cooperative
ligands
coordination
sphere
metal
center
order
improve
catalytic
activity
under
photochemical,
electrochemical
or
thermal
conditions.
Moreover,
cooperativity
crucial
easy
transition
first
row
based
catalysis,
we
have
seen
years.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(10), С. 4094 - 4120
Опубликована: Янв. 1, 2022
This
review
explores
and
summarises
synthetic
methods
that
may
be
used
to
prepare
heterocyclic
ring
systems
from
non-activated
ketones,
considers
their
potential
value
towards
the
synthesis
of
natural
product-inspired
compound
collections.
Catalysts,
Год журнала:
2020,
Номер
10(7), С. 773 - 773
Опубликована: Июль 11, 2020
Our
planet
urgently
needs
sustainable
solutions
to
alleviate
the
anthropogenic
global
warming
and
climate
change.
Homogeneous
catalysis
has
potential
play
a
fundamental
role
in
this
process,
providing
novel,
efficient,
at
same
time
eco-friendly
routes
for
both
chemicals
energy
production.
In
particular,
pincer-type
ligation
shows
promising
properties
terms
of
long-term
stability
selectivity,
as
well
allowing
mild
reaction
conditions
low
catalyst
loading.
Indeed,
pincer
complexes
have
been
applied
plethora
chemical
processes,
such
hydrogen
release,
CO2
capture
conversion,
N2
fixation,
biomass
valorization
synthesis
high-value
fuels.
work,
we
show
main
advances
last
five
years
use
transition
metal
key
catalytic
processes
aiming
more
ChemCatChem,
Год журнала:
2019,
Номер
12(7), С. 1891 - 1902
Опубликована: Дек. 21, 2019
Abstract
Acceptorless
dehydrogenative
coupling
(ADC)
has
emerged
as
a
powerful
tool
in
the
chemists’
arsenal
for
construction
of
various
carbon‐carbon
and
carbon‐heteroatom
bonds.
These
protocols
are
highly
atom
economical
environmentally
benign
they
do
not
require
pre‐functionalized
starting
material
produce
only
dihydrogen
(and
water)
by‐product.
This
technique,
coupled
with
Earths’
abundant
less
toxic
manganese
catalysis,
can
prove
to
be
vital
strategy
generation
molecular
complexity
from
simple
materials.
Manganese
catalyzed
DHC
been
growing
interest,
low‐
high‐valent
catalysts
have
developed.
were
demonstrated
show
excellent
catalytic
activity
formation
carbon‐carbon,
bonds,
cascade
reactions.
In
this
mini‐review,
we
would
like
highlight
recent
progress
that
made
ADC
Journal of the American Chemical Society,
Год журнала:
2019,
Номер
141(6), С. 2398 - 2403
Опубликована: Янв. 11, 2019
A
recent
study
showed
that
a
Mn-pincer
could
catalyze
the
acceptorless
dehydrogenative
coupling
of
nitriles
and
alcohols
to
yield
acrylonitriles.
The
reaction
mechanism
proposed
in
work
contained
some
intermediates
that,
most
cases,
were
not
characterized.
Moreover,
one
involved
charged
separation,
which
is
unlikely
apolar
solvents.
To
clarify
this
critical
reaction,
we
decided
perform
DFT
study.
Our
results
prove
existence
cooperative
effect
metal
ligand
several
steps
catalytic
cycle.
We
also
find
presence
equilibria
between
isomeric
where
water,
or
same
alcohol
reagent,
takes
part
assisting
proton
transfer.
Furthermore,
have
analyzed
charge-separated
structure
experimentally
found
nearly
pure
covalent
bond
two
expected
moieties.
Finally,
Knoevenagel
condensation
step
generates
acrylonitrile
be
rate-determining
step.
The Journal of Organic Chemistry,
Год журнала:
2019,
Номер
84(12), С. 7927 - 7935
Опубликована: Май 22, 2019
A
general
and
chemoselective
catalytic
alkylation
of
nitriles
using
a
homogeneous
nonprecious
manganese
catalyst
is
presented.
This
reaction
uses
naturally
abundant
alcohols
readily
available
as
coupling
partners.
The
tolerates
wide
range
functional
groups
heterocyclic
moieties,
efficiently
providing
useful
cyanoalkylated
products
with
water
the
only
side
product.
Importantly,
methanol
can
be
used
C1
source
C-methylation
achieved.
mechanistic
investigations
support
multiple
role
metal-ligand
catalyst,
dehydrogenative
activation
alcohol,
α-C-H
nitrile,
hydrogenation
in-situ-formed
unsaturated
intermediate.
