Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(13), P. 2540 - 2545
Published: March 28, 2024
An
oxygen-dependent
ligand-controlled
chemoselective
synthesis
of
vinyl
nitriles
and
E-olefins
by
coupling
a
variety
alcohols
benzyl
cyanides,
catalyzed
well-characterized,
air-stable,
easy-to-prepare
Fe(II)
catalyst
(1a)
bearing
redox-active
arylazo
pincer
(L1a)
is
reported.
The
azo-moiety
the
ligand
backbone
acts
as
an
electron
hydrogen
reservoir,
enabling
1a
to
efficiently
produce
broad
spectrum
in
moderate
good
yields
selectively
under
oxygen
argon
atmosphere,
respectively.
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.
ChemCatChem,
Journal Year:
2019,
Volume and Issue:
12(7), P. 1891 - 1902
Published: Dec. 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
ACS Catalysis,
Journal Year:
2018,
Volume and Issue:
9(1), P. 479 - 484
Published: Dec. 13, 2018
Base-metal-catalyzed
dehydrogenative
cross-coupling
of
primary
alcohols
to
form
cross-esters
as
major
products,
liberating
hydrogen
gas,
is
reported.
The
reaction
catalyzed
by
a
pincer
complex
earth-abundant
manganese
in
the
presence
catalytic
base,
without
any
acceptor
or
oxidant.
Mechanistic
insight
indicates
that
dearomatized
actual
catalyst,
and
indeed
this
independently
prepared
catalyzes
under
neutral
conditions.
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.
Organometallics,
Journal Year:
2021,
Volume and Issue:
40(9), P. 1213 - 1220
Published: April 20, 2021
The
catalytic
reduction
of
carbon
dioxide
is
a
process
growing
interest
for
the
use
this
simple
and
abundant
molecule
as
renewable
building
block
in
C1-chemical
synthesis
hydrogen
storage.
well-defined,
bench-stable
alkylcarbonyl
Mn(I)
bis(phosphine)
complex
fac-[Mn(CH2CH2CH3)(dippe)(CO)3]
[dippe
=
1,2-bis(diisopropylphosphino)ethane]
was
tested
an
efficient
selective
non-precious-metal
precatalyst
hydrogenation
CO2
to
formate
under
mild
conditions
(75
bar
total
pressure,
80
°C),
presence
Lewis
acid
co-catalyst
(LiOTf)
base
(DBU).
Mechanistic
insight
into
reaction
provided
by
means
density
functional
theory
(DFT)
calculations.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(8), P. 5250 - 5265
Published: March 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.
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
57(46), P. 15143 - 15147
Published: Oct. 26, 2018
Abstract
Reported
herein
is
a
general
and
efficient
dual‐deoxygenative
coupling
of
primary
alcohols
with
2‐arylethanols
catalyzed
by
well‐defined
Mn/PNP
pincer
complex.
This
reaction
the
first
example
catalytic
dual‐deoxygenation
using
non‐noble‐metal
catalyst.
Both
deoxygenative
homocoupling
(17
examples)
their
cross‐coupling
other
(20
proceeded
smoothly
to
form
corresponding
alkenes
dehydrogenation
deformylation
sequence.
