Herein,
we
report
a
sodium
tert-butoxide-promoted
reduction
of
N-heteroarenes
using
ammonia
borane
and
dimethyl
sulfoxide
(DMSO)
under
mild
reaction
conditions.
This
method
demonstrates
broad
functional
group
compatibility
across
diverse
N-heteroarene
substrates.
Notably,
substituting
DMSO
with
deuterated
DMSO-d6
enables
the
synthesis
C3-deuterated
1,2,3,4-tetrahydroquinolines
remarkable
positional
selectivity.
Mechanistic
investigations
indicate
that
protons
are
derived
from
both
DMSO.
strategy
establishes
novel
environmentally
benign
approach
for
(deuterated)
N-heterocycles,
offering
practical
advantages
in
terms
operational
simplicity
sustainable
Inorganic Chemistry,
Год журнала:
2024,
Номер
63(12), С. 5681 - 5688
Опубликована: Март 14, 2024
Three
new
POM-based
compounds,
with
formulae
[Na0.63Ag3(Htba)2.37(tba)0.63(H2O)2(PMo12O40)]·4H2O
(Ag3PMo),
[Ag4(Htba)4(H2O)2(PMo12O40)](NO3)·H2O
(Ag4PMo),
and
[Ag3(Htba)2(tba)(PW12O40)0.5](NO3)0.5·13H2O
(Ag3PW),
were
prepared
a
3-(4H-1,2,4-triazol-4-yl)benzoic
acid
(Htba)
ligand,
Keggin-type
anions
([PMo12O40]3–/[PW12O40]3–),
silver
ion
(Ag+).
The
structural
features
of
these
compounds
are
particularly
different
from
the
multinuclear
subunits,
which
[Ag3(tba)3]
clusters
in
Ag3PMo,
[Ag4(tba)3]
chains
Ag4PMo,
[Ag3(tba)3]2
Ag3PW,
connected
by
multidonor
atom
tba
ligands
Ag+
ions.
Meanwhile,
polyanions
act
as
polydentate
to
link
adjacent
Ag-tba
metal–organic
units
expand
their
spatial
dimensions.
These
heterogeneous
catalysts,
exhibit
high
stability
excellent
catalytic
activity
construct
benzimidazoles.
Ag3PMo
could
efficiently
catalyze
condensation
benzene-1,2-diamines
benzaldehydes
produce
benzimidazoles
good
yields.
In
addition,
be
reused
up
7
times
was
suitable
for
gram-scale
reactions.
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 5344 - 5355
Опубликована: Март 26, 2024
In
this
work,
a
Keggin-type
platinum
substituted
polyoxometalate
(POM)
is
constructed
by
the
reaction
of
monolacunary
phosphotungstate
precursor
[PW11O39]7–
with
chloroplatinic
acid.
The
as-obtained
tetrabutylammonium
salt
(TBA-PWPt)
demonstrates
that
dimeric
Pt2+
ions
are
incorporated
into
POM
frameworks
and
linked
two
anions.
Notably,
once
Pt-substituted
anion
reduced
H2,
anion-stabilizing
Pt
nanocatalysts
generated,
which
greatly
facilitates
forming
oxygen
vacancies
adjacent
to
Pt0
species.
show
superior
catalytic
activity
stability
for
selective
hydrogenation
quinoline
1,2,3,4-tetrahydroquinoline
in
water.
Detailed
investigations
elucidate
stronger
adsorption
on
surface
H2
activated
at
POMs-Pt
interface
site.
Moreover,
density
functional
theory
(DFT)
calculations
H2O
adsorbed
interfacial
then
undergoes
homolytic
dissociation
produce
hydroxyl
group
(OH–)
hydride
(H–)
H–
species
transferred
N-containing
pyridine
ring
hydrogenation,
OH–
help
promote
heterolytic
H+
Sequentially,
produced
proton
groups
generate
H2O,
cycle
completed.
Crystal Growth & Design,
Год журнала:
2024,
Номер
24(8), С. 3473 - 3482
Опубликована: Апрель 8, 2024
Adjusting
the
Lewis
acid–base
sites
in
MOF-based
catalysts
to
meet
demand
for
catalytic
CO2
chemical
fixation
is
a
huge
challenge.
Herein,
highly
robust
rectilinear
{Zn3}-based
metal–organic
framework
of
{[Zn3(TNTNB)2(4,4′-bip)(H2O)2]·5DMF·9H2O}n
(NUC-80)
was
generalized
from
solvothermal
condition
(H3TNTNB
=
1,3,5-tri(3-nitro-4-carboxyphenyl)-2,4,6-trinitrobenzene,
4,4′-bip
4,4′-bipyridine).
Activated
NUC-80a
not
only
owns
large
void
volume
(58%)
and
two
kinds
solvent-accessible
channels:
rhombic-like
(ca.
14.24
×
14.57
Å)
along
axis
rectangular-like
11.72
14.48
b
axis,
but
also
functionalized
by
rich
metal
plentiful
nitro
groups
on
its
inner
surface.
Performed
experiments
confirmed
that
could
efficiently
catalyze
cycloaddition
reaction
with
epoxides
Knoevenagel
condensations
aldehydes
malononitrile
under
mild
conditions
high
turnover
frequency
(TOF).
Hence,
this
work
provides
nitro-functionalized
cluster-based
nanoporous
wide
range
potential
applications
such
as
catalysis,
gas
adsorption,
separation.
ACS Central Science,
Год журнала:
2023,
Номер
9(8), С. 1692 - 1701
Опубликована: Июль 27, 2023
The
development
of
efficient
heterogeneous
catalysts
with
multiselectivity
(e.g.,
enantio-
and
chemoselectivity)
has
long
been
sought
after
but
limited
progress
being
made
so
far.
To
achieve
chemoselectivity
in
a
system,
as
inspired
by
enzymes,
we
illustrate
herein
an
approach
creating
enzyme-mimic
region
(EMR)
within
the
nanospace
metal–organic
framework
(MOF)
exemplified
context
incorporating
chiral
frustrated
Lewis
pair
(CFLP)
into
MOF
tailored
pore
environment.
Due
to
high
density
EMR
featuring
active
site
CFLP
auxiliary
sites
hydroxyl
group/open
metal
vicinity
CFLP,
resultant
EMR@MOF
demonstrated
excellent
catalysis
performance
hydrogenation
α,β-unsaturated
imines
afford
β-unsaturated
amines
yields
chemoselectivity.
role
regulating
was
proved
observation
catalyst–substrate
interaction
experimentally,
which
also
rationalized
computational
results.
This
work
not
only
contributes
new
platform
for
multiselective
opens
promising
avenue
develop
challenging
yet
important
transformations.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(26), С. 17924 - 17930
Опубликована: Июнь 20, 2024
Nitroalkanes
serve
as
essential
intermediates
in
the
synthesis
of
pharmaceuticals,
agrochemicals,
and
functional
materials.
To
date,
nitroalkanes
are
mainly
prepared
from
homogeneous
catalysts
such
noble
transition
metal
with
poor
recyclability.
Herein,
we
propose
a
metal–organic
framework-frustrated
Lewis
pair
(MOF-FLP)
heterogeneous
catalyst
for
selectively
reducing
nitroolefins
to
under
moderate
reaction
conditions.
MOF
enrichment
effect
can
significantly
improve
catalytic
efficiency
compared
FLP
catalysts.
Benefiting
strong
interaction
between
MOF,
MOF-FLP
exhibits
outstanding
This
work
not
only
provides
convenient
route
nitroalkane
but
also
showcases
potential
porous
catalysts,
offering
inspiration
future
design
strategies.
