Inorganic Chemistry,
Год журнала:
2021,
Номер
61(2), С. 1195 - 1206
Опубликована: Дек. 28, 2021
A
well-defined
and
very
active
single-component
manganese(II)
catalyst
system
for
the
hydrosilylation
of
aldehydes
ketones
is
presented.
First,
reaction
5-(2,4,6-iPr3C6H2)-2-[N-(2,6-iPr2C6H3)formimino]pyrrolyl
potassium
(KL)
[MnCl2(Py)2]
afforded
binuclear
2-iminopyrrolyl
pyridine
chloride
complex
[Mn2{κ2N,N'-5-(2,4,6-iPr3C6H2)-NC4H2-2-C(H)═N(2,6-iPr2C6H3)}2(Py)2(μ-Cl)2]
1.
Subsequently,
alkylation
1
with
LiCH2SiMe3
respective
(trimethylsilyl)methyl-Mn(II)
[Mn{κ2N,N'-5-(2,4,6-iPr3C6H2)-NC4H2-2-C(H)═N(2,6-iPr2C6H3)}(Py)CH2SiMe3]
2
in
a
good
yield.
Complexes
were
characterized
by
elemental
analysis,
1H
NMR
spectroscopy,
Evans'
method,
FTIR
single-crystal
X-ray
diffraction.
While
crystal
structure
has
been
identified
as
entity,
which
Mn(II)
centers
present
pentacoordinate
coordination
spheres,
that
corresponds
to
monomer
distorted
tetrahedral
geometry.
Complex
proved
be
precatalyst
atom-economic
several
under
mild
conditions,
maximum
turnover
frequency
95
min-1,
via
silyl-Mn(II)
mechanistic
route,
asserted
combination
experimental
theoretical
efforts,
silanes
cleanly
converted
alcoholic
products
high
yields.
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.
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
ACS Catalysis,
Год журнала:
2019,
Номер
10(1), С. 197 - 202
Опубликована: Ноя. 21, 2019
A
highly
selective
Mn(I)-catalyzed
alkenylation
of
arenes
and
heteroarenes
with
1,3-diynes
is
described.
The
reported
transformation
overcomes
regio-,
chemo-,
stereoselectivity
challenges
associated
the
use
these
coupling
partners.
Both
symmetrical
unsymmetrical
diynes
can
be
applied
in
this
protocol,
affording
single
isomers
not
only
synthesis
1,3-enynes
but
also
one-step
preparation
pyrroles
furans.
This
simple
strategy
features
wide
functional
group
tolerance,
good
reproducibility,
preparative
scale
utility.
manganese
catalyst
plays
a
crucial
role
C–H
activation
enabling
high
selectivity
previously
challenging
internal
alkynes.
Furthermore,
synthetic
value
method
highlighted
by
diverse
postsynthesis
functionalizations
final
products.
ACS Catalysis,
Год журнала:
2021,
Номер
11(5), С. 2786 - 2794
Опубликована: Фев. 15, 2021
Herein
we
report
the
synthesis
of
primary
and
secondary
amines
by
nitrile
hydrogenation,
employing
a
borrowing
hydrogenation
strategy.
A
class
phosphine-free
manganese(I)
complexes
bearing
sulfur
side
arms
catalyzed
reaction
under
mild
conditions,
where
ammonia–borane
is
used
as
source
hydrogen.
The
synthetic
protocol
chemodivergent,
final
product
either
or
amine,
which
can
be
controlled
changing
catalyst
structure
polarity
medium.
significant
advantage
this
method
that
operates
without
externally
added
base
other
additives
well
obviates
use
high-pressure
dihydrogen
gas
required
for
reactions.
Utilizing
method,
wide
variety
symmetric
asymmetric
were
synthesized
in
high
yields.
mechanistic
study
involving
kinetic
experiments
high-level
DFT
computations
revealed
both
outer-sphere
dehydrogenation
inner-sphere
predominantly
operative
catalytic
cycle.
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.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(14), С. 4024 - 4040
Опубликована: Янв. 1, 2024
This
review
provides
a
comprehensive
overview
of
metal
catalysis
in
photo-electrochemical
systems,
discussing
reaction
mechanisms
and
offering
prospects
for
this
triadic
catalytic
mode.
ACS Catalysis,
Год журнала:
2021,
Номер
11(12), С. 7060 - 7069
Опубликована: Июнь 2, 2021
Controlling
the
selectivity
in
a
hydroamination
reaction
is
an
extremely
challenging
yet
highly
desirable
task
for
diversification
of
amines.
In
this
article,
selective
formal
anti-Markovnikov
allyl
alcohols
presented.
It
enables
versatile
synthesis
valuable
γ-amino
alcohol
building
blocks.
A
phosphine-free
Earth's
abundant
manganese(I)
complex
catalyzed
under
hydrogen-borrowing
conditions.
vast
range
aliphatic,
aromatic
amines,
drug
molecules,
and
natural
product
derivatives
underwent
successful
with
primary
secondary
allylic
excellent
functional
group
tolerance
(57
examples).
The
catalysis
could
be
performed
on
gram
scale
has
been
applied
molecules.
mechanistic
studies
revealed
metal–ligand
bifunctionality
as
well
hemilability
ligand
backbone
key
design
principle
success
catalysis.
Organic Letters,
Год журнала:
2021,
Номер
23(12), С. 4624 - 4629
Опубликована: Июнь 9, 2021
Co(III)-catalyzed
highly
regio-
and
stereoselective
direct
C6
olefination
of
2-pyridones
with
alkynes
has
been
developed
the
assistance
chelation.
Upon
variation
reaction
conditions,
react
well
diaryl
via
a
olefination/directing
group
migration
pathway
to
give
tetrasubstituted
6-vinyl-2-pyridones,
but
C6-H
terminal
works
effectively
afford
only
C6-olefinated
2-pyridones.
A
judicious
choice
solvent
an
additive
is
crucial
for
catalysis.
The
protocols
feature
100%
atom
economy,
excellent
site
selectivity,
high
stereoselectivity,
ample
substrate
scope,
good
compatibility
functional
groups.
Synthetic
applications
are
demonstrated,
experimental
studies
density
theory
calculations
conducted
gain
mechanistic
insight
into
two
transformations.