Angewandte Chemie,
Год журнала:
2024,
Номер
136(13)
Опубликована: Фев. 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.
Chemical Reviews,
Год журнала:
2023,
Номер
123(12), С. 7692 - 7760
Опубликована: Май 10, 2023
Site-predictable
and
chemoselective
C–H
bond
functionalization
reactions
offer
synthetically
powerful
strategies
for
the
step-economic
diversification
of
both
feedstock
fine
chemicals.
Many
transition-metal-catalyzed
methods
have
emerged
selective
activation
bonds.
However,
challenges
regio-
chemoselectivity
with
application
to
highly
complex
molecules
bearing
significant
functional
group
density
diversity.
As
molecular
complexity
increases
within
structures
risks
catalyst
intolerance
limited
applicability
grow
number
groups
potentially
Lewis
basic
heteroatoms.
Given
abundance
bonds
already
diversified
such
as
pharmaceuticals,
natural
products,
materials,
design
selection
reaction
conditions
tolerant
catalysts
has
proved
critical
successful
direct
functionalization.
such,
innovations
formation
carbon–carbon
been
discovered
developed
overcome
these
limitations.
This
review
highlights
progress
made
metal-catalyzed
C–C
forming
including
alkylation,
methylation,
arylation,
olefination
targets.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(23)
Опубликована: Апрель 7, 2023
The
reactivity
of
metal-hydride
complexes
can
be
harnessed
by
the
modification
ancillary
ligands.
With
aim
improving
hydride-donor
ability
key
Mn-H
intermediate
and
reducing
steric
hindrance,
we
herein
report
rational
design
a
versatile
efficient
NHC-based
NNC-pincer
Mn
catalyst
for
hydrogenation
reactions.
This
newly
developed
exhibited
higher
activity
than
corresponding
NNP-pincer
owing
to
its
reduced
hindrance
enhanced
σ-bonding
orbital
energy
level
through
π-antibonding
interaction.
Using
this
highly
active
catalyst,
rich
array
polar
unsaturated
compounds
(>80
examples)
including
esters,
N-heteroarenes,
amides,
carbonates,
urea
derivatives,
were
successfully
hydrogenated
under
relatively
mild
conditions.
work
represents
rare
example
general
phosphine-free
Mn-catalyzed
system.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(17), С. 11801 - 11810
Опубликована: Апрель 16, 2024
The
direct
double
dehydrogenation
from
primary
amines
to
nitriles
without
an
oxidant
or
hydrogen
acceptor
is
both
intriguing
and
challenging.
In
this
paper,
we
describe
a
non-noble
metal
catalyst
capable
of
realizing
such
transformation
with
high
efficiency.
A
cobalt-centered
N,N-bidentate
complex
was
designed
employed
as
metal–ligand
cooperative
catalyst.
Detailed
kinetic
studies,
control
experiments,
DFT
calculations
revealed
the
crucial
hydride
transfer,
proton
evolution
processes.
Finally,
tandem
outer-sphere/inner-sphere
mechanism
proposed
for
through
imine
intermediate.
In
the
past
decade,
computational
tools
have
become
integral
to
catalyst
design.
They
continue
offer
significant
support
experimental
organic
synthesis
and
catalysis
researchers
aiming
for
optimal
reaction
outcomes.
More
recently,
data-driven
approaches
utilizing
machine
learning
garnered
considerable
attention
their
expansive
capabilities.
This
Perspective
provides
an
overview
of
diverse
initiatives
in
realm
design
introduces
our
automated
tailored
high-throughput
silico
exploration
chemical
space.
While
valuable
insights
are
gained
through
methods
analysis
space,
degree
automation
modularity
key.
We
argue
that
integration
data-driven,
modular
workflows
is
key
enhancing
homogeneous
on
unprecedented
scale,
contributing
advancement
research.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(13)
Опубликована: Фев. 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.
Chemical Communications,
Год журнала:
2023,
Номер
59(13), С. 1757 - 1768
Опубликована: Янв. 1, 2023
In
this
feature
article,
we
discuss
how
the
different
aspects
of
complex
catalytic
mechanisms
manifest
themselves
in
commonly
accepted
performance
metrics.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(35)
Опубликована: Июль 3, 2023
The
use
of
bis(NHC)
manganese(I)
complexes
3
as
catalysts
for
the
hydrogenation
esters
was
investigated.
For
that
purpose,
a
series
has
been
synthesized
via
an
improved
two
step
procedure
utilizing
bis(NHC)-BEt3
adducts.
By
applying
with
KHBEt3
additive,
various
aromatic
and
aliphatic
were
hydrogenated
successfully
at
mild
temperatures
low
catalyst
loadings,
highlighting
efficiency
novel
catalytic
system.
versatility
developed
system
further
demonstrated
by
other
substrate
classes
like
ketones,
nitriles,
N-heteroarenes
alkenes.
Mechanistic
experiments
DFT
calculations
indicate
inner
sphere
mechanism
loss
one
CO
ligand
reveal
role
BEt3
cocatalyst.
ACS Catalysis,
Год журнала:
2024,
Номер
14(6), С. 4082 - 4092
Опубликована: Март 1, 2024
A
series
of
Mo
complexes
bearing
inexpensive
bidentate
bis(NHC)
ligands
have
been
synthesized
and
characterized
by
NMR
IR
spectroscopy
as
well
single
crystal
XRD
analysis.
These
proved
to
be
efficient
for
the
catalytic
hydrogenation
aliphatic
aromatic
esters
(>35
examples)
operating
at
low
catalyst
loadings
(0.5–2
mol
%)
temperatures
(80–120
°C).
Various
functional
groups,
e.g.,
C═C
double
bonds,
nitriles,
alcohols,
tertiary
amines,
halides,
acetals,
heteroaromatic
substrates,
lactones,
diesters,
are
tolerated
optimal
system.
Based
on
spectroscopic
investigations,
control
experiments
DFT
computations
a
non-bifunctional
outer-sphere
mechanism
is
proposed.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
29(2)
Опубликована: Окт. 4, 2022
Manganese-catalyzed
hydrogenation
reactions
have
aroused
widespread
interest
in
recent
years.
Among
the
catalytic
systems
described,
especially
PNP-
and
NNP-Mn
pincer
catalysts
been
reported
for
of
aldehydes,
ketones,
nitriles,
aldimines
esters.
Furthermore,
compounds
are
efficient
hydrogenolysis
less
reactive
amides,
ureas,
carbonates,
carbamates.
Herein,
synthesis
application
specific
imidazolylaminophosphine
ligands
corresponding
Mn
complexes
described.
These
new
characterized
studied
by
a
combination
experimental
theoretical
investigations,
their
activities
tested
several
with
good
to
excellent
performance.
Especially,
reduction
N-heterocycles
can
be
performed
under
very
mild
conditions.
