ChemCatChem,
Год журнала:
2021,
Номер
13(22), С. 4751 - 4758
Опубликована: Сен. 2, 2021
Abstract
Benzothiazole‐doped
porous
organic
polymers
(
POP‐MBTS
)
were
synthesized
from
a
copolymerization
reaction
of
2‐(6‐(4‐vinylphenyl)pyridin‐2‐yl)benzo[
d
]thiazole
with
divinylbenzene.
The
corresponding
POP‐MBTS‐Ir
was
obtained
and
fully
characterized
using
SEM,
TEM,
EDS,
TGA,
XPS,
N
2
sorption
isotherms,
which
disclosed
that
this
catalyst
has
high
surface
area,
hierarchical
porosity,
thermodynamic
stability.
Importantly,
revealed
catalytic
activity
for
ten
different
kinds
borrowing
hydrogen
dehydrogenation
reactions
in
water
good
recovery
performance.
Furthermore,
mechanistic
investigations
conducted
the
synthesis
triazine
derivatives.
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.
Chemical Reviews,
Год журнала:
2024,
Номер
124(9), С. 6078 - 6144
Опубликована: Апрель 17, 2024
Alcohols
are
abundant
and
attractive
feedstock
molecules
for
organic
synthesis.
Many
methods
their
functionalization
require
them
to
first
be
converted
into
a
more
activated
derivative,
while
recent
years
have
seen
vast
increase
in
the
number
of
complexity-building
transformations
that
directly
harness
unprotected
alcohols.
This
Review
discusses
how
transition
metal
catalysis
can
used
toward
this
goal.
These
broadly
classified
three
categories.
Deoxygenative
functionalizations,
representing
derivatization
C–O
bond,
enable
alcohol
act
as
leaving
group
formation
new
C–C
bonds.
Etherifications,
characterized
by
O–H
represent
classical
reactivity
has
been
modernized
include
mild
reaction
conditions,
diverse
partners,
high
selectivities.
Lastly,
chain
reactions
described,
wherein
acts
mediator
formal
C–H
alkyl
backbone.
Each
these
classes
transformation
will
discussed
context
intermolecular
arylation,
alkylation,
related
reactions,
illustrating
alcohols
harnessed
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
59(1), С. 215 - 220
Опубликована: Окт. 25, 2019
Highly
selective
β-methylation
of
alcohols
was
achieved
using
an
earth-abundant
first
row
transition
metal
in
the
air
stable
molecular
manganese
complex
[Mn(CO)
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
59(4), С. 1485 - 1490
Опубликована: Ноя. 19, 2019
Abstract
We
report
an
earth‐abundant‐metal‐catalyzed
double
and
single
methylation
of
alcohols.
A
manganese
catalyst,
which
operates
at
low
catalyst
loadings
short
reaction
times,
mediates
these
reactions
efficiently.
broad
scope
primary
secondary
alcohols,
including
purely
aliphatic
examples,
1,2‐aminoalcohols
can
be
methylated.
Furthermore,
alcohol
for
the
synthesis
pharmaceuticals
has
been
demonstrated.
The
system
tolerates
many
functional
groups
among
them
hydrogenation‐sensitive
examples
upscaling
is
easily
achieved.
Mechanistic
investigations
are
indicative
a
borrowing
hydrogen
or
autotransfer
mechanism
involving
bimetallic
K‐Mn
catalyst.
accepts
as
proton
hydride
from
alcohols
efficiently
reacts
with
chalcone
via
transfer.
Journal of the American Chemical Society,
Год журнала:
2019,
Номер
141(44), С. 17487 - 17492
Опубликована: Окт. 29, 2019
A
method
for
the
synthesis
of
substituted
cycloalkanes
was
developed
using
diols
and
secondary
alcohols
or
ketones
via
a
cascade
hydrogen
borrowing
sequence.
non-noble
air-stable
manganese
catalyst
(2
mol
%)
used
to
perform
this
transformation.
Various
1,5-pentanediols
(3-4
equiv)
(1
were
investigated
prepare
collection
cyclohexanes
in
diastereoselective
fashion.
Similarly,
cyclopentane,
cyclohexane,
cycloheptane
rings
constructed
from
1,4-butanediol,
1,5-pentanediol,
1,6-hexanediol,
sterically
hindered
following
(4
+
1),
(5
(6
1)
strategy,
respectively.
This
reaction
provides
an
atom
economic
methodology
construct
two
C-C
bonds
at
single
carbon
center
generating
high-value
readily
available
as
feedstock
earth-abundant
metal
catalyst.
Chemical Communications,
Год журнала:
2021,
Номер
57(69), С. 8534 - 8549
Опубликована: Янв. 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.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(26)
Опубликована: Апрель 21, 2023
A
homogeneous
manganese-catalyzed
cross-coupling
of
two
secondary
alcohols
for
the
divergent
synthesis
γ-disubstituted
and
β-disubstituted
ketones
is
reported.
Employing
well-defined
Mn-MACHOPh
as
catalyst,
this
novel
protocol
has
a
broad
substrate
scope
with
good
functional
group
tolerance
affords
diverse
library
valuable
disubstituted
in
moderate
to
yields.
The
strong
influence
reaction
temperature
on
selective
formation
alcohol
products
was
theorized
preliminary
DFT
studies.
Studies
have
shown
that
Gibbs
free
energy
thermodynamically
more
favourable
than
corresponding
at
lower
temperature.
ACS Catalysis,
Год журнала:
2020,
Номер
10(4), С. 2615 - 2626
Опубликована: Янв. 24, 2020
Herein,
we
report
the
stereoselective
synthesis
of
(1
+
n)-membered
cycloalkane
from
methyl
ketone
and
1,n-diol.
A
manganese(I)
complex
bearing
a
phosphine-free
ligand
catalyzed
reaction,
which
involved
formation
two
C–C
bonds
via
sequence
intermolecular-
intramolecular-borrowing
hydrogenation
reactions.
It
produces
2
mol
water
as
sole
byproduct,
making
process
atom
economical
environmentally
benign.
Multisubstituted
cycloalkanes
were
obtained
in
good
to
excellent
yields
with
very
high
selectivities.
thorough
mechanistic
analysis
by
high-level
DFT
computation
rationalizes
choice
pincer
establishes
role
hemilability
for
this
efficient
transformation.
Advanced Synthesis & Catalysis,
Год журнала:
2020,
Номер
362(8), С. 1602 - 1650
Опубликована: Янв. 29, 2020
Abstract
Manganese‐catalysed
reactions
have
attracted
great
attention
recently
due
to
the
high
relative
abundance
and
cheap
eco‐friendly
behaviour.
Applications
of
manganese
catalysis
in
cross‐dehydrogenative
coupling
are
among
hottest
areas
since
90%
contributions
very
recent.
Dehydrogenation
alcohols
using
Mn‐pincer
systems
is
highly
explored
nowadays
for
cross‐coupling
synthesise
a
variety
products
Mn‐catalysed
C−H
activation,
radical
applied
dehydrogenative
couplings
various
synthons.
This
review
focuses
on
synthesis
synthetically
as
well
biologically
important
motifs
such
carbonyl
compounds,
olefins,
nitrogen
heterocycles,
amines,
imines,
etc.
manganese‐catalysed
reactions.
magnified
image