Abstract
The
selective
oxidation
of
5‐hydroxymethylfurfural
(HMF)
toward
2,5‐furandicarboxylic
acid
(FDCA)
offers
a
promising
green
pathway
to
obtain
monomers
for
the
synthesis
biodegradable
plastics.
However,
developing
high‐selectivity
catalyst
and
understanding
catalytic
mechanism
are
still
great
challenge.
Here,
we
synthesize
nRu/FeCo
2
O
4
with
Ru
nanoparticles
loaded
on
FeCo
.
presents
excellent
HMF
activity
100%
conversion
efficiency
99%
FDCA
yield
under
optimized
conditions.
Density‐functional
theory
calculations
further
reveal
structure
matching
high‐selective
FDCA,
that
is,
loading
in
provides
more
suitable
configuration
adsorption
two‐side
chains
HMF,
which
could
optimize
energy
thus
increase
reactivity.
In
short,
this
work
strategy
designing
dual‐active‐site
relay
oxidize
‐CHO
C‐OH
groups
achieve
highly‐selective
FDCA.
Abstract
A
sustainable
upgrading
of
renewable
bulk
materials,
obtained
by
decomposition
biomass
lignocellulose,
could
facilitate
their
use
in
the
industrial
production
chemicals.
Homogeneous
ruthenium
catalysis
plays
a
fundamental
role
this
area.
The
review
deals
with
upgradation
lignocellulosic
molecules
through
formation
new
C−C
and
C−N
bonds.
Selected
examples
catalytic
bond
forming
reactions
reported
until
mid
2023,
include:
(a)
dehydrogenative
based
couplings
alcohols,
(b)
reductive
amination
carbonyl
compounds,
(c)
direct
C−H
functionalization
(hetero)aromatic
compounds.
These
approaches
fulfill
requirements
sustainability:
application
occurs
without
any
previous
substrate
activation,
thus
reducing
waste.
New
chemicals
containing
intrinsic
molecular
structure
lignocellulose
substrates,
showed
broad
range
applications:
green
fuels,
hydrogen
carriers,
monomers
polymers,
intermediates
fine
pharmaceuticals.
results
discussed
inspire
reader
to
improve
valorization
process,
terms
bio‐substrate
scope
as
well
product
complexity,
more
strategic
applications
methods.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 1, 2024
Abstract
Biomass
has
been
identified
as
the
ultimate
sustainable
resource
for
all
carbon‐based
consumer
products
of
chemical
industries
in
future.
Its
catalytic
conversion
leads
to
formation
various
platform
chemicals
that
could
partially
or
even
fully
replace
fossil‐based
building
blocks
have
currently
used
synthetic
processes.
Among
these
compounds,
levulinic
acid
(LA)
recognized
a
member
“Top
Value
Added
Chemicals
from
Biomass”
and
attracted
significant
attention
since
seminal
paper
reported
by
Werpy
Petersen
2004.
This
review
summarizes
properties,
recent
advances,
developments
chemistry
acid.
The
production
LA
both
plant
animal‐based
carbohydrate
feedstocks
via
5‐hydroxymethylfurfural
furfuryl
alcohol
is
discussed
mechanistic
perspective,
highlighting
intrinsic
molecular‐level
limitations
formation.
efficiencies
recently
developed
systems
are
also
summarized
compared.
Furthermore,
into
high‐value‐added
downstream
chemicals,
including
its
role
synthesis
complex
molecular
structures,
overviewed.
section
reactions
points
view
transformations
on
carbonyl‐,
carboxy‐,
methyl‐,
methylene
functional
groups.
functionalities
with
C
−,
N
O
S
‐nucleophiles,
alcohols,
amines,
organometallic
reagents,
oxygen
etc.
were
thematically
summarized.
Our
outlooks
highlight
challenges
opportunities
associated
extensive
research
area
organic
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(25)
Опубликована: Апрель 22, 2023
Abstract
The
atom‐
and
step‐efficient
synthesis
of
chiral
fused
tricyclic
lactams
from
readily
available
ketoesters
using
cheap
ammonium
salts
as
the
nitrogen
source
is
reported.
This
ruthenium‐catalyzed
system
operates
through
an
efficient
tandem
dynamic
kinetic
asymmetric
reductive
amination
(ARA)/lactamization
produces
in
high
yields
with
excellent
diastereo‐
enantioselectivity
(up
to
>99
%
ee,
>20
:
1
dr
98
yield).
robust
method
was
also
applied
concise
key
intermediates
rivastigmine
analogues
N‐heterocyclic
carbene
catalysts.
Abstract
Catalytic
transformation
of
renewable
biomass
into
value-added
chemicals
is
an
appealing
strategy
to
upgrade
resources.
Due
the
presence
abundant
oxygen-containing
groups
such
as
hydroxyl
and
aldehyde,
its
derived
platform
molecules
have
been
served
ideal
starting
feedstock
synthesize
valuable
N-containing
through
reductive
amination.
In
this
mini
review,
we
overviewed
recent
advances
in
amination
several
key
bio-platform
including
carboxylic
acids,
furfural,
5-hydroxylmethyl
furfural
levulinic
acid,
with
a
focus
on
production
amino
furan
amines
pyrrolidones
using
thermocatalysis,
electrocatalysis
or
photocatalysis.
Moreover,
functions
active
sites
reaction
mechanisms
different
catalytic
systems
are
discussed
get
insights
factors
Angewandte Chemie,
Год журнала:
2023,
Номер
135(25)
Опубликована: Апрель 22, 2023
Abstract
The
atom‐
and
step‐efficient
synthesis
of
chiral
fused
tricyclic
lactams
from
readily
available
ketoesters
using
cheap
ammonium
salts
as
the
nitrogen
source
is
reported.
This
ruthenium‐catalyzed
system
operates
through
an
efficient
tandem
dynamic
kinetic
asymmetric
reductive
amination
(ARA)/lactamization
produces
in
high
yields
with
excellent
diastereo‐
enantioselectivity
(up
to
>99
%
ee,
>20
:
1
dr
98
yield).
robust
method
was
also
applied
concise
key
intermediates
rivastigmine
analogues
N‐heterocyclic
carbene
catalysts.
