Organic Chemistry Frontiers,
Год журнала:
2018,
Номер
5(22), С. 3250 - 3255
Опубликована: Янв. 1, 2018
Here
we
report
the
first
base-metal
catalyzed
dehydrogenative
coupling
of
primary
(aromatic,
heteroaromatic,
and
aliphatic)
secondary
alcohols
with
methyl-N-heteroaromatics
to
form
various
C(sp3)-alkylated
N-heteroaromatics.
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.
Advanced Synthesis & Catalysis,
Год журнала:
2018,
Номер
360(17), С. 3233 - 3238
Опубликована: Июнь 29, 2018
Abstract
Herein,
we
report
a
very
simple
and
inexpensive
catalytic
system
based
on
Earth's
abundant
transition
metal
manganese
bench‐stable
phosphine‐free
NNN‐pincer
ligand
for
an
atom‐efficient
α‐alkylations
of
ketones
with
primary
alcohols
via
hydrogen‐autotransfer
C−C
bond
formation
protocol.
The
precatalyst
could
be
generated
in
situ
activated
by
using
amount
base
under
milder
conditions.
A
range
were
efficiently
diversified
broad
good
to
excellent
isolated
yields.
Remarkably,
this
catalyst
also
employed
the
synthesis
quinoline
derivatives
2‐aminobenzyl
alcohol
as
alkylating
agent.
later
reaction
is
highly
benign
producing
only
hydrogen
water
byproducts.
magnified
image
ACS Catalysis,
Год журнала:
2018,
Номер
8(10), С. 9226 - 9231
Опубликована: Авг. 24, 2018
The
manganese(I)
complex
bearing
a
bidentate
hydrazone
ligand
efficiently
catalyzes
the
α-alkylations
of
nitrile
using
primary
alcohols
as
alkylating
agents.
α-Functionalized
nitriles
were
selectively
obtained
in
good
to
excellent
yields.
reaction
is
environmentally
benign,
producing
water
sole
byproduct.
Both
benzylic
and
aliphatic
could
be
used
functional
groups
tolerated.
Chemical Communications,
Год журнала:
2018,
Номер
55(3), С. 314 - 317
Опубликована: Дек. 10, 2018
The
direct
α-methylation
of
ketones
with
methanol
under
hydrogen
borrowing
conditions
using
a
well-defined
manganese
PN3P
complex
as
pre-catalyst
was,
for
the
first
time,
achieved.
reactions
typically
proceed
at
120
°C
20
h
3
mol%
loading
and
in
presence
NaOtBu
(50
mol%)
base.
scope
reaction
was
extended
to
esters.
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
Organometallics,
Год журнала:
2019,
Номер
38(8), С. 1815 - 1825
Опубликована: Апрель 12, 2019
The
application
of
nontoxic,
earth-abundant
transition
metals
in
place
costly
noble
is
a
paramount
goal
catalysis
and
especially
interesting
if
the
air-
moisture-stable
ligand
scaffold
used.
Herein,
we
report
synthesis
amines/imines
directly
from
alcohol
amines
via
hydrogen
autotransfer
or
acceptorless
dehydrogenation
catalyzed
by
well-defined
phosphine-free
Mn
complexes.
Both
imines
can
be
obtained
same
set
alcohols
using
catalyst,
only
tuning
reaction
conditions.
amount
nature
base
are
found
to
highly
important
aspect
for
observed
selectivity.
primary
secondary
have
been
employed
as
substrates
N-alkylation
reaction.
As
highlight,
showed
chemoselective
resveratrol
derivatives.
Furthermore,
Mn-catalyzed
dehydrogenative
structurally
2,3-dihydro-1H-perimidines
has
also
demonstrated.
Density
functional
theory
calculations
were
carried
out
model
path
calculate
profile.
Nature Communications,
Год журнала:
2020,
Номер
11(1)
Опубликована: Янв. 30, 2020
Abstract
The
development
of
cost-effective,
sustainable,
and
efficient
catalysts
for
liquid
organic
hydrogen
carrier
systems
is
a
significant
goal.
However,
all
the
reported
relied
on
use
precious
metal
catalysts.
Herein,
system
based
non-noble
catalysis
was
established.
Mn-catalyzed
dehydrogenative
coupling
methanol
N
,
’-dimethylethylenediamine
to
form
’-(ethane-1,2-diyl)bis(
-methylformamide),
reverse
hydrogenation
reaction
constitute
storage
with
theoretical
capacity
5.3
wt%.
A
rechargeable
could
be
achieved
by
subsequent
resulting
dehydrogenation
mixture
regenerate
H
2
-rich
compound.
maximum
selectivity
amide
formation
97%.
