Based
around
the
idea
of
searching
for
sustainable
alternatives
to
fossil
sources
manufacturing
fuels
and
chemical
products,
this
doctoral
thesis
addresses
development
new
catalytic
processes
centered
on
glycerol
valorization,
which
is
main
by-product
biodiesel
synthesis.In
sense,
aim
focused
using
it
as
a
carbon
source
generate
nitrogen
heterocycles
industrial
interest,
specifically,
produce
2methylpiperazine
2-methylpyrazine.However,
due
low
reactivity
severe
reaction
conditions
necessary
carry
out
transformations
towards
these
N-heterocycles,
previous
detailed
research
optimize
understand
selective
dehydration
process
hydroxyacetone
(or
acetol)
was
undertaken.Through
obtaining
intermediate
compound,
has
been
possible
develop
efficient
production
under
reasonably
moderate
conditions.In
regard,
Cu-Mg-Al
hydrotalcite
precursors
give
rise
family
materials
based
mixed
oxides
capable,
if
their
composition
adequately
optimized,
carrying
acetol
continuously
with
yields
≈40%.In
addition,
catalysts
are
stable
more
than
8
hours
operational
conditions,
showing
excellent
regeneration
capacity
reusability.In
same
way,
through
combination
characterization
studies,
interesting
mix
acid-base
redox
centers
exhibited
by
allowed
advancing
significantly
in
state
art
regarding
understanding
reaction.Hence,
verify
fundamental
role
Cu
species
and,
Cu(I)
present
catalysts,
generation
glyceraldehyde
critical
production.Similarly,
acid
catalyst
facilitate
first
adsorption
glycerol,
thus
accelerating
reaction.However,
need
achieve
higher
productivities
from
stand
chance
succeed
overall
strategy
motivated
study
second
copper
oxide
supported
different
metal
(SiO2,
Al2O3
ZrO2)
combining
Lewis
high
exposure.The
proper
selection
optimization
lead
reaching,
several
them,
60%
much
concentrations
starting
feed.
Green Chemistry,
Год журнала:
2017,
Номер
19(11), С. 2477 - 2481
Опубликована: Янв. 1, 2017
NHC-catalysis
enables
the
successful
functionalisation
of
glycerol
through
a
telescoped
reaction
strategy
involving
carbonation
and
subsequent
oxidative
esterification.
Chemistry - A European Journal,
Год журнала:
2017,
Номер
23(58), С. 14416 - 14419
Опубликована: Авг. 31, 2017
The
acetate
complex
Ru(OAc)2
(DiPPF)
(2)
obtained
from
(PPh3
)2
(1)
and
1,1'-bis(diisopropylphosphino)ferrocene
reacts
cleanly
with
formaldehyde
affording
(CO)(DiPPF)
(3)
in
high
yield.
monocarbonyl
3
(0.4-2
mol
%)
efficiently
catalyzes
the
N-alkylation
of
primary
secondary
alkyl
aromatic
amines
using
alcohols
ROH
(R=Et,
nPr,
nBu,
PhCH2
)
under
mild
reaction
conditions
(30-100
°C)
an
alcohol/amine
molar
ratio
10-100.
Formation
monohydride
RuH(OAc)(CO)(DiPPF)
(4)
has
been
observed
by
iPrOH
presence
NEt3
at
RT
through
equilibrium
reaction.
Catalysis Today,
Год журнала:
2023,
Номер
424, С. 114296 - 114296
Опубликована: Июль 18, 2023
The
solvent-free
acetalization
of
glycerol
with
acetone
was
investigated
using
as
catalyst
UAV-59,
a
Coordination
Polymer
based
on
nitrilo(trimethylphosphonic
acid)
and
Gd3+,
at
25
°C
55
°C,
various
glycerol/acetone
(Gly/Ace)
molar
ratios.
reaction
yielded
solketal,
five-membered
acetal,
2,2-dimethyl-1,3-dioxan-5-ol,
six-membered
acetal.
UAV-59's
catalytic
activity
influenced
by
temperature,
the
highest
conversion
(94%)
achieved
1/10
Gly/Ace
ratio,
5%
catalyst.
selectivity
for
solketal
remained
consistent
(95%
-
98%)
across
all
conditions.
Reaction
kinetics
profiles
were
compared,
stability
assessed,
results
benchmarked
against
Metal
Organic
Framework
catalysts
from
literature.
heterogeneous
nature
catalysis
confirmed
through
leaching
tests,
catalyst's
chemical
features
analyzed
ATR
FT-IR
spectra
X-ray
diffraction
patterns,
indicating
that
crystalline
structure
preserved
during
reaction.
Organic Process Research & Development,
Год журнала:
2024,
Номер
28(8), С. 3414 - 3422
Опубликована: Июль 25, 2024
We
report
herein
the
development
and
scale
up
of
an
Ir-catalyzed
N-alkylation
reaction
between
a
4-bromopyridin-2-amine
(1)
(4-(5-(1,1-difluoroethyl)-1,2,4-oxadiazol-3-yl)bicyclo[2.2.2]octan-1-yl)methanol
(2)
proceeding
via
borrowing
hydrogen
process.
The
traditional
approach
alcohol
oxidation
followed
by
reductive
amination
posed
challenges
that
are
attributed
to
poor
nucleophilicity
2-aminopyridine
derivative
resulting
in
lower
isolated
yields.
Several
catalysts
bases
were
evaluated
for
successful
1
with
2,
Ir
(III)
catalyst
combination
LiOt-Bu
as
base
was
found
provide
optimal
conversion.
process
successfully
demonstrated
on
1.5
kg
afforded
>70%
yield
3
without
need
sealed
reactor
or
any
other
specialized
equipment.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(22), С. 16510 - 16521
Опубликована: Ноя. 4, 2024
Aliphatic
allylic
amines
are
present
in
a
large
number
of
complex
and
pharmaceutically
relevant
molecules.
The
direct
amination
electrophiles
serves
as
the
most
common
method
toward
preparation
these
motifs.
However,
use
feedstock
reaction
components
(allyl
alcohol
aliphatic
amine)
transformations
remains
great
challenge.
Such
challenge
primarily
stems
from
high
Lewis
basicity
steric
hindrance
amines,
addition
to
low
reactivity
alcohols.
Herein,
we
report
general
solution
challenges.
developed
protocol
allows
an
efficient
allyl
alcohols
with
sterically
bulky
presence
inexpensive
earth-abundant
molybdenum
complex.
This
simple
economic
also
enables
regioselective
branched
amination;
practicality
was
shown
efficient,
scaled-up
synthesis
several
drugs.
ChemSusChem,
Год журнала:
2020,
Номер
13(8), С. 2007 - 2011
Опубликована: Фев. 3, 2020
Abstract
Highly
efficient
Ru‐catalyzed
selective
C−C
or
C−O
bond
cleavage
of
polyols
(e.g.,
crude
glycerol)
for
N
‐hydroxyethylation
‐acetonylation
amines
was
achieved
through
the
hydrogen‐borrowing
approach.
A
variety
were
transformed
to
desired
amino
alcohols/ketones
in
moderate‐to‐excellent
yields,
opening
up
new
avenues
generation
oxygenated
pharmaceuticals
and
fine
chemicals
from
renewable
raw
materials.
The
use
redox‐active
catalysts
containing
bisphosphine/thienylmethylamine
ligands
allows
this
system
be
operated
selectively
under
both
basic
acidic
conditions.
European Journal of Organic Chemistry,
Год журнала:
2020,
Номер
2020(20), С. 3030 - 3040
Опубликована: Апрель 16, 2020
A
robust
alcohol
amination
protocol
using
common
saturated
amines
and
primary
alcohols
as
starting
materials
is
described.
The
reactions
are
catalyzed
by
combination
of
dichloro(
p
‐cymene)ruthenium(II)
dimer
precatalyst
with
triphenylphosphine
ligand,
the
excess
substrate
or
toluene
functioning
solvent.
catalyst
ligand
residues
can
be
precipitated
from
reaction
media
addition
hexane
cold
diethyl
ether,
followed
precipitation
isolation
product
a
hydrochloride
salt.
