Nature Communications,
Journal Year:
2020,
Volume and Issue:
11(1)
Published: March 6, 2020
Catalytic
hydrogenation
or
transfer
of
quinolines
was
thought
to
be
a
direct
strategy
access
dihydroquinolines.
However,
the
challenge
is
control
chemoselectivity
and
regioselectivity.
Here
we
report
an
efficient
partial
system
operated
by
cobalt-amido
cooperative
catalyst,
which
converts
1,2-dihydroquinolines
reaction
with
H
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
121(2), P. 567 - 648
Published: Sept. 17, 2020
Heterogeneous
catalysis
involves
solid-state
catalysts,
among
which
metal
nanoparticles
occupy
an
important
position.
Unfortunately,
no
two
from
conventional
synthesis
are
the
same
at
atomic
level,
though
such
regular
can
be
highly
uniform
nanometer
level
(e.g.,
size
distribution
∼5%).
In
long
pursuit
of
well-defined
nanocatalysts,
a
recent
success
is
atomically
precise
nanoclusters
protected
by
ligands
in
range
tens
to
hundreds
atoms
(equivalently
1–3
nm
core
diameter).
More
importantly,
have
been
crystallographically
characterized,
just
like
protein
structures
enzyme
catalysis.
Such
merge
features
homogeneous
catalysts
ligand-protected
centers)
and
enzymes
protein-encapsulated
clusters
few
bridged
ligands).
The
with
their
total
available
constitute
new
class
model
hold
great
promise
fundamental
research,
including
dependent
activity,
control
catalytic
selectivity
structure
surface
ligands,
structure–property
relationships
atomic-level,
insights
into
molecular
activation
mechanisms,
identification
active
sites
on
nanocatalysts.
This
Review
summarizes
progress
utilization
for
These
nanocluster-based
enabled
heterogeneous
research
single-atom
single-electron
levels.
Future
efforts
expected
achieve
more
exciting
understanding
tailoring
design
high
activity
under
mild
conditions.
Advanced Energy Materials,
Journal Year:
2021,
Volume and Issue:
12(5)
Published: Dec. 22, 2021
Abstract
Strain
engineering
of
nanomaterials,
namely,
designing,
tuning,
or
controlling
surface
strains
nanomaterials
is
an
effective
strategy
to
achieve
outstanding
performance
in
different
for
their
various
applications.
This
article
summarizes
recent
progress
and
achievements
the
development
strain‐rich
electrocatalysts
(SREs)
applications
field
electrochemical
energy
conversion
technologies.
It
starts
from
definition
lattice
strains,
followed
by
classification
where
mechanisms
strain
formation
reported
methods
regulate
related
are
elaborated.
The
SRE
characterization
techniques
overviewed,
focusing
deeply
on
clarification
strain‐property
relationship
these
SREs.
Their
electrocatalytic
reactions
further
highlighted,
including
hydrogen
evolution
reaction,
oxygen
reduction
alcohol
oxidation
carbon
dioxide
nitrogen
reaction.
Related
reaction
SREs
interpreted
after
taking
catalytic
performance,
as
well
between
properties
into
account.
challenges
future
opportunities
finally
outlined
discussed
together
with
potential
fields.
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.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(11), P. 6100 - 6111
Published: March 10, 2023
Privileged
diphosphine
ligands
that
chelate
many
transition
metals
to
form
stable
chelation
complexes
are
essential
in
a
variety
of
catalytic
processes.
However,
the
exact
identity
catalytically
active
moieties
remains
ambiguous
because
chelated
metal
catalysts
may
undergo
rearrangement
during
catalysis
produce
monophosphine-metal
complexes,
which
hard
isolate
and
evaluate
activities.
By
taking
advantage
isolation
two
phosphorus
atoms,
we
demonstrate
here
successful
construction
chiral
monophosphine-Ir/Ru
covalent
organic
frameworks
(COFs)
for
enantioselective
hydrogenation.
condensation
tetraaldehyde
enantiopure
MeO-BIPHEP
linear
aromatic
diamines,
prepare
homochiral
two-dimensional
COFs
with
ABC
stacking,
P
atoms
each
separated
fixed
far
apart.
Post-synthetic
metalations
thus
afford
single-site
Ir/Ru-monophosphine
catalysts,
contrast
homogeneous
analogues,
demonstrated
excellent
recyclable
performance
asymmetric
hydrogenation
quinolines
β-ketoesters,
affording
up
99.9%
enantiomeric
excess.
Owing
fact
porous
catalyst
is
capable
adsorbing
concentrating
hydrogen,
reactions
promoted
under
ambient/medium
pressure,
typically
performed
high
pressure
catalysis.
This
work
not
only
shows
diphosphines
can
be
centers
but
also
provides
new
strategy
types
privileged
phosphine-based
heterogeneous
catalysts.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
60(10), P. 5108 - 5113
Published: Nov. 26, 2020
Abstract
The
non‐noble
metal‐catalyzed
asymmetric
hydrogenation
of
N‐heteroaromatics,
quinolines,
is
reported.
A
new
chiral
pincer
manganese
catalyst
showed
outstanding
catalytic
activity
in
the
affording
high
yields
and
enantioselectivities
(up
to
97
%
ee).
turnover
number
3840
was
reached
at
a
low
loading
(S/C=4000),
which
competitive
with
most
effective
noble
metal
catalysts
for
this
reaction.
precise
regulation
enantioselectivity
were
ensured
by
π–π
interaction.
Nature Communications,
Journal Year:
2020,
Volume and Issue:
11(1)
Published: June 26, 2020
Asymmetric
hydrogenation
of
α,β-unsaturated
acids
catalyzed
by
noble
metals
has
been
well
established,
whereas,
the
asymmetric
with
earth-abundant-metal
was
rarely
reported.
Here,
we
describe
a
cobalt-catalyzed
carboxylic
acids.
By
using
chiral
cobalt
catalyst
bearing
electron-donating
diphosphine
ligand,
high
activity
(up
to
1860
TON)
and
excellent
enantioselectivity
>99%
ee)
are
observed.
Furthermore,
is
successfully
applied
broad
spectrum
acids,
such
as
various
α-aryl
α-alkyl
cinnamic
acid
derivatives,
α-oxy-functionalized
α-substituted
acrylic
heterocyclic
(30
examples).
The
synthetic
utility
protocol
highlighted
synthesis
key
intermediates
for
drugs
(6
cases).
Preliminary
mechanistic
studies
reveal
that
carboxy
group
may
be
involved
in
control
reactivity
through
an
interaction
metal
centre.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(20), P. 11384 - 11390
Published: Feb. 19, 2021
Abstract
Chiral
carboxylic
acids
are
important
compounds
because
of
their
prevalence
in
pharmaceuticals,
natural
products
and
agrochemicals.
Asymmetric
hydrogenation
α,β‐unsaturated
has
been
widely
recognized
as
one
the
most
efficient
synthetic
approaches
to
afford
such
compounds.
Although
related
asymmetric
di‐
trisubstituted
unsaturated
with
noble
metals
is
well
established,
challenging
tetrasubstituted
rarely
reported.
We
demonstrate
enantioselective
cyclic
acyclic
via
cobalt(II)
catalysis.
This
protocol
showed
broad
substrate
scope
gave
chiral
good
yields
excellent
enantiocontrol
(up
98
%
yield
99
ee
).
Combined
experimental
computational
mechanistic
studies
support
a
Co
II
catalytic
cycle
involving
migratory
insertion
σ‐bond
metathesis
processes.
DFT
calculations
reveal
that
enantioselectivity
may
originate
from
steric
effect
between
phenyl
groups
ligand
substrate.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(48), P. 20071 - 20076
Published: Nov. 19, 2021
Here
we
report
that
chiral
Mn(I)
complexes
are
capable
of
H-P
bond
activation.
This
activation
mode
enables
a
general
method
for
the
hydrophosphination
internal
and
terminal
α,β-unsaturated
nitriles.
Metal-ligand
cooperation,
strategy
previously
not
considered
catalytic
activation,
is
at
base
mechanistic
action
Mn(I)-based
catalyst.
Our
computational
studies
support
stepwise
mechanism
provide
insight
into
origin
enantioselectivity.