Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(11), P. 4386 - 4464
Published: Jan. 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.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(7), P. 2742 - 2747
Published: March 23, 2021
The
reduction
of
nitroarenes
to
anilines
as
well
azobenzenes
hydrazobenzenes
using
a
single
base-metal
catalyst
is
reported.
hydrogenation
reactions
are
performed
with
an
air-and
moisture-stable
manganese
and
proceed
under
relatively
mild
reaction
conditions.
transformation
tolerates
broad
range
functional
groups,
affording
aniline
derivatives
in
high
yields.
Mechanistic
studies
suggest
that
the
proceeds
via
bifunctional
activation
involving
metal–ligand
cooperative
catalysis.
Chemical Communications,
Journal Year:
2021,
Volume and Issue:
57(69), P. 8534 - 8549
Published: Jan. 1, 2021
Manganese
catalyzed
hydrogen
transfer
reactions
enabled
net
reductions
and
cascade
CC-
CN-bond
formation
reactions.
The
success
is
aided
by
multifunctional
ligand
design
namely
metal–ligand
bifunctionality,
hemilability,
redox
non-innocence.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(22), P. 15013 - 15053
Published: Nov. 6, 2023
Methanol
is
a
fundamental
feedstock
and
widely
used
in
the
chemical
petroleum
industries.
It
can
serve
as
C1
source
to
make
variety
of
C–C
C–N
bond
formation
dehydrogenative
coupling
products,
which
have
important
applications
natural
products
drug
discovery.
A
high
hydrogen
content
(12.5
wt%)
methanol
makes
it
an
effective
H2
donor
for
transfer
hydrogenation
various
reducible
functional
groups.
plethora
transition
metal-based
processes
been
developed
using
methanol.
Notably,
recent
review
articles
focused
on
aspect
However,
more
updated
that
examines
challenges
both
C1-source
H2-source
organic
transformations
contributing
concept
economy
has
not
presented
yet.
This
Review
summarizes
(homogeneous,
heterogeneous,
photo-)
catalyst
system
C-,
N-,
O-methylation
ketones,
alcohols,
amides,
nitriles,
heterocyclic
compounds,
sulfones,
amines,
sulfonamides
direct
N-methylation
nitro
compounds
under
borrowing
strategy
N-formylation
amines
acceptorless
dehydrogenation
source.
also
covers
insights
into
reaction
mechanisms
role
carefully
selected
ligands
metal
catalysis
activation
incorporation
-CD3,
methylation
molecules.
Moreover,
describes
groups
such
aldehydes,
alkynes,
with
detail.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(4), P. 2245 - 2259
Published: Feb. 8, 2023
Catalytic
reduction
reactions
using
methanol
as
a
transfer
hydrogenating
agent
is
gaining
significant
attention
because
this
simple
alcohol
inexpensive
and
produced
on
bulk
scale.
Herein,
we
report
the
catalytic
utilization
of
hydrogen
source
for
different
functional
organic
compounds
such
nitroarenes,
olefins,
carbonyl
compounds.
The
key
to
success
transformation
use
commercially
available
Pt/C
catalyst,
which
enabled
hydrogenation
series
functionalized
nitroarenes-to-anilines,
alkenes-to-alkanes,
aldehydes-to-alcohols
both
solvent
donor.
practicability
Pt-based
protocol
showcased
by
demonstrating
catalyst
recycling
reusability
well
reaction
upscaling.
In
addition,
system
was
also
adaptable
N-methylation
N-alkylation
anilines
via
borrowing
process.
This
work
provides
flexible
approach
prepare
variety
value-added
products
from
readily
methanol,
Pt/C,
other
starting
materials.
Molecules,
Journal Year:
2023,
Volume and Issue:
28(22), P. 7541 - 7541
Published: Nov. 11, 2023
Catalytic
transfer
hydrogenation
has
emerged
as
a
pivotal
chemical
process
with
transformative
potential
in
various
industries.
This
review
highlights
the
significance
of
catalytic
hydrogenation,
reaction
that
facilitates
hydrogen
from
one
molecule
to
another,
using
distinct
source
presence
catalyst.
Unlike
conventional
direct
offers
numerous
advantages,
such
enhanced
safety,
cost-effective
donors,
byproduct
recyclability,
catalyst
accessibility,
and
for
asymmetric
particularly
chiral
ligands.
Moreover,
diverse
range
donor
molecules
utilized
this
have
been
explored,
shedding
light
on
their
unique
properties
impact
systems
mechanism
elucidation
some
reactions.
Alcohols
methanol
isopropanol
are
prominent
demonstrating
remarkable
efficacy
reductions.
Formic
acid
irreversible
preventing
occurrence
reverse
reactions,
is
extensively
compound
synthesis.
Unconventional
donors
1,4-cyclohexadiene
glycerol
shown
good
efficiency
reducing
unsaturated
compounds,
additionally
serving
green
solvent
transformations.
The
compatibility
these
catalysts,
substrates,
conditions
were
all
discussed.
Furthermore,
paper
outlines
future
trends
which
include
utilization
biomass-derived
exploration
storage
materials
metal-organic
frameworks
(MOFs),
development
activity
eco-friendly
solvents
ionic
liquids.
Innovative
heating
methods,
base
materials,
continued
research
into
catalyst-hydrogen
interactions
aimed
shape
enhancing
its
selectivity
across
industries
applications.
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(4), P. 2072 - 2081
Published: Jan. 17, 2024
Coordinatively
unsaturated
complexes
are
interesting
from
a
fundamental
level
for
their
formally
empty
coordination
site
and,
in
particular,
catalytic
perspective
as
they
provide
opportunities
substrate
binding
and
transformation.
Here,
we
describe
the
synthesis
of
novel
underligated
ruthenium
complex
[Ru(cym)(N,N')]
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(13)
Published: Feb. 1, 2024
Abstract
The
synthesis
of
mono‐
N
‐methylated
aliphatic
primary
amines
has
traditionally
been
challenging,
requiring
noble
metal
catalysts
and
high‐pressure
H
2
for
achieving
satisfactory
yields
selectivity.
Herein,
we
developed
an
approach
the
selective
coupling
methanol
amines,
without
hydrogen,
using
a
manganese‐based
catalyst.
Remarkably,
up
to
98
%
with
broad
substrate
scope
were
achieved
at
low
catalyst
loadings.
Notably,
due
weak
base‐catalyzed
alcoholysis
formamide
intermediates,
our
novel
protocol
not
only
obviates
addition
but
also
prevents
side
secondary
‐methylation,
supported
by
control
experiments
density
functional
theory
calculations.
