Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(13)
Published: Feb. 1, 2024
Abstract
The
synthesis
of
mono‐
N
‐methylated
aliphatic
primary
amines
has
traditionally
been
challenging,
requiring
noble
metal
catalysts
and
high‐pressure
H
2
for
achieving
satisfactory
yields
selectivity.
Herein,
we
developed
an
approach
the
selective
coupling
methanol
amines,
without
hydrogen,
using
a
manganese‐based
catalyst.
Remarkably,
up
to
98
%
with
broad
substrate
scope
were
achieved
at
low
catalyst
loadings.
Notably,
due
weak
base‐catalyzed
alcoholysis
formamide
intermediates,
our
novel
protocol
not
only
obviates
addition
but
also
prevents
side
secondary
‐methylation,
supported
by
control
experiments
density
functional
theory
calculations.
Green Chemistry,
Journal Year:
2022,
Volume and Issue:
24(6), P. 2602 - 2612
Published: Jan. 1, 2022
Porous
polypyridine-oxadiazole
supported
iridium
catalysts
(PPO-Ir)
revealed
high
catalytic
activity
for
the
reaction
of
dimethyl-6-aminouracil
(including
1,3-dimethylbarbituric
acid,
2-aminobenzylamine)
with
alcohols.
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.
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:
2024,
Volume and Issue:
63(13)
Published: Feb. 1, 2024
Abstract
The
synthesis
of
mono‐
N
‐methylated
aliphatic
primary
amines
has
traditionally
been
challenging,
requiring
noble
metal
catalysts
and
high‐pressure
H
2
for
achieving
satisfactory
yields
selectivity.
Herein,
we
developed
an
approach
the
selective
coupling
methanol
amines,
without
hydrogen,
using
a
manganese‐based
catalyst.
Remarkably,
up
to
98
%
with
broad
substrate
scope
were
achieved
at
low
catalyst
loadings.
Notably,
due
weak
base‐catalyzed
alcoholysis
formamide
intermediates,
our
novel
protocol
not
only
obviates
addition
but
also
prevents
side
secondary
‐methylation,
supported
by
control
experiments
density
functional
theory
calculations.
