Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
134(26)
Published: April 19, 2022
Abstract
A
unique
family
of
chiral
peraza
N
6
‐macrocyclic
ligands,
which
are
conformationally
rigid
and
have
a
tunable
saddle‐shaped
cavity,
is
described.
Utilizing
their
manganese(I)
complexes,
the
first
example
earth‐abundant
transition
metal‐catalyzed
asymmetric
formal
anti‐Markovnikov
hydroamination
allylic
alcohols
was
realized,
providing
practical
access
to
synthetically
important
γ‐amino
in
excellent
yields
enantioselectivities
(up
99
%
yield
98
ee).
The
single‐crystal
structure
Mn
I
complex
indicates
that
manganese
atom
coordinates
with
dialkylamine
moiety
bidentate
fashion.
Further
DFT
calculations
revealed
five
six
nitrogen
atoms
ligand
were
engaged
multiple
noncovalent
interactions
Mn,
an
isopropanol
molecule,
β‐amino
ketone
intermediate
via
coordination,
hydrogen
bonding,
and/or
CH⋅⋅⋅π
state,
showing
remarkable
role
macrocyclic
framework.
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.
The Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
87(13), P. 8351 - 8367
Published: June 21, 2022
Herein,
we
report
a
simple,
phosphine-free,
and
inexpensive
catalytic
system
based
on
manganese(II)
complex
for
synthesizing
different
important
N-heterocycles
such
as
quinolines,
pyrroles,
pyridines
from
amino
alcohols
ketones.
Several
control
experiments,
kinetic
studies,
DFT
calculations
were
carried
out
to
support
the
plausible
reaction
mechanism.
We
also
detected
two
potential
intermediates
in
cycle
using
ESI-MS
analysis.
Based
these
metal-ligand
cooperative
mechanism
was
proposed.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(26)
Published: April 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.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(14), P. 4024 - 4040
Published: Jan. 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.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(14)
Published: March 7, 2024
Abstract
Direct
asymmetric
hydrogenation
(AH)
and
transfer
(ATH)
are
among
the
most
efficient
approaches
to
produce
chiral
building
blocks.
Recently,
these
types
of
transformations
have
witnessed
a
shift
towards
use
molecular
catalysts
based
on
earth‐abundant
transition
metals
due
their
ready
availability,
economic
advantage,
novel
properties.
With
particular
regard
manganese,
catalyst
development
has
seen
both
efficiency
substrate
scope
in
AH
ATH
greatly
improved,
with
emergence
large
number
well‐defined
Mn‐complexes
employed
this
field.
The
reaction
includes
C=O
bonds,
reduction
C=N
bonds
reductive
C=C
bonds.
Herein,
our
survey
area
focuses
catalytic
activity
such
complexes,
versatility
routes
convert
substrates
target
molecules.
We
consider
collected
findings
article
will
be
helpful
reader
by
providing
an
insight
into
ligand
design,
thereby
aiding
future
development.
Moreover,
review
is
aimed
at
highlighting
remarkable
progress
made
last
seven
years
manganese
complexes
for
enantioselective
reduction.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(26)
Published: April 19, 2022
A
unique
family
of
chiral
peraza
N6
-macrocyclic
ligands,
which
are
conformationally
rigid
and
have
a
tunable
saddle-shaped
cavity,
is
described.
Utilizing
their
manganese(I)
complexes,
the
first
example
earth-abundant
transition
metal-catalyzed
asymmetric
formal
anti-Markovnikov
hydroamination
allylic
alcohols
was
realized,
providing
practical
access
to
synthetically
important
γ-amino
in
excellent
yields
enantioselectivities
(up
99
%
yield
98
ee).
The
single-crystal
structure
MnI
complex
indicates
that
manganese
atom
coordinates
with
dialkylamine
moiety
bidentate
fashion.
Further
DFT
calculations
revealed
five
six
nitrogen
atoms
ligand
were
engaged
multiple
noncovalent
interactions
Mn,
an
isopropanol
molecule,
β-amino
ketone
intermediate
via
coordination,
hydrogen
bonding,
and/or
CH⋅⋅⋅π
state,
showing
remarkable
role
macrocyclic
framework.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(19), P. 12444 - 12457
Published: Sept. 28, 2022
Tandem
transformation
of
α,β-unsaturated
ketones
to
α-methylated
by
utilizing
methanol
as
both
the
hydrogen
and
C1
sources
is
reported
in
presence
a
phosphine-free
bis-N-heterocyclic
carbene-Mn(I)
(bis-NHC-Mn(I))
catalyst.
The
dehydrogenative
coupling
between
produces
corresponding
along
with
1
equiv
formaldehyde
water.
Among
different
bis-NHC-Mn(I)
complexes,
ethyl
wingtip-substituted
complex
triflate
counteranion
showed
highest
catalytic
activity.
This
system
was
highly
effective
for
reductive
methylation
wide
variety
substrates
including
aromatic,
heteroaromatic,
aliphatic
straight
chains
containing
ketones.
Notably,
this
methodology
led
synthesis
pharmaceutically
important
drug
molecules
such
eperisone
lanperisone.
Several
control
experiments,
kinetic
studies,
Hammett
density
functional
theory
(DFT)
calculations
were
carried
out
understand
tandem
process.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(17)
Published: Feb. 27, 2023
Herein,
we
report
a
manganese-catalyzed
three-component
coupling
of
secondary
alcohols,
primary
alcohols
and
methanol
for
the
synthesis
β,β-methylated/alkylated
alcohols.
Using
our
method,
series
1-arylethanol,
benzyl
alcohol
derivatives,
undergo
sequential
efficiently
to
construct
assembled
with
high
chemoselectivity
in
moderate
good
yields.
Mechanistic
studies
suggest
that
reaction
proceeds
via
methylation
benzylated
intermediate
generate
final
product.
ACS Omega,
Journal Year:
2022,
Volume and Issue:
7(42), P. 37008 - 37038
Published: Oct. 11, 2022
In
recent
years,
many
manganese-based
homogeneous
catalytic
precursors
have
been
developed
as
powerful
alternatives
in
organic
synthesis.
Among
these,
the
hydrofunctionalizations
of
unsaturated
C–C
bonds
correspond
to
outstanding
ways
afford
compounds
with
more
versatile
functional
groups,
which
are
commonly
used
building
blocks
production
fine
chemicals
and
feedstock
for
industrial
field.
Herein,
we
present
an
account
Mn-catalyzed
alkenes
alkynes
main
objective
finding
mechanistic
tendencies
that
could
serve
a
platform
works
come.
