ACS Sustainable Chemistry & Engineering,
Journal Year:
2024,
Volume and Issue:
12(20), P. 7791 - 7801
Published: May 3, 2024
The
development
of
sustainable
and
economical
catalytic
systems
for
the
hydration
nitriles
into
amides
is
great
industrial
significance.
In
this
work,
amorphous
Fe0.7Cu0.3Ox-300,
synthesized
by
a
simple
melting
method,
presented
high
activity
nitrile
in
water,
without
any
additives.
Characterization
mechanism
experiments
indicated
that
surface
oxygen
Fe0.7Cu0.3Ox-300
acts
as
Brønsted
base
sites,
enhancing
dissociation
H2O.
Fe–Cu
interaction
within
catalyst
facilitates
formation
active
Fe
species
with
higher
valence
states,
serving
Lewis
acidic
sites
molecule
adsorption
activation.
Notably,
achieved
efficient
synthesis
various
aromatic,
aliphatic,
heteroaromatic
yields
(20
products),
also
showcasing
good
scalability
stability.
Moreover,
limited
solubility
most
water
further
simplifies
process,
allowing
simultaneous
purification.
This
study
manifests
potential
large-scale
applications
amide
synthesis,
aligned
principles
chemistry.
Organic Process Research & Development,
Journal Year:
2022,
Volume and Issue:
26(10), P. 2894 - 2899
Published: Sept. 9, 2022
The
undesired
reaction
between
carbodiimides
(peptide
coupling
reagent)
and
OxymaPure
additive),
which
takes
place
in
very
low
extension
during
peptide
bond
formation,
is
dependent
on
the
steric
hindrance
around
carbodiimide
backbone.
Carbodiimides
containing
tertiary
substituents
N
such
as
di-tert-butylcarbodiimide
do
not
activate
carboxylic
group
properly;
presence
of
secondary
case
diisopropylcarbodiimide
(DIC)
leads
to
formation
oxadiazole
HCN;
finally,
primary
render
an
adduct
oxadiazine
no
HCN.
tert-Butylethylcarbodiimide
(TBEC),
a
hybrid
substituents,
with
concomitant
Furthermore,
TBEC
outperforms
DIC
terms
yield
minimization
racemization
it
demonstrated
herein.
Communications Chemistry,
Journal Year:
2022,
Volume and Issue:
5(1)
Published: Sept. 26, 2022
Abstract
In
living
organisms,
enzyme
catalysis
takes
place
in
aqueous
media
with
extraordinary
spatiotemporal
control
and
precision.
The
mechanistic
knowledge
of
related
approaches
creating
a
suitable
microenvironment
for
efficient
chemical
transformations
have
been
an
important
source
inspiration
the
design
biomimetic
artificial
catalysts.
However,
“nature-like”
environments,
it
has
proven
difficult
catalysts
to
promote
effective
transformations.
Besides,
over
reaction
rate
selectivity
are
smart
application
purposes.
These
can
be
achieved
via
incorporation
stimuli-responsive
features
into
structure
catalytic
systems.
Here,
we
summarize
such
systems
whose
activity
switched
‘on’
or
‘off’
by
stimuli
environments.
We
describe
switchable
capable
performing
organic
classification
accordance
stimulating
agent.
Switchable
environments
provides
new
possibilities
development
materials
biomedicine
biology.
Moreover,
engineering
expected
grow
coming
years
further
broadening
its
diverse
fields.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(39)
Published: May 6, 2024
Abstract
Peptide−oligonucleotide
conjugates
(POCs)
are
covalent
architectures
composed
of
a
DNA
or
RNA
molecules
linked
to
peptide.
These
constructs
have
found
widespread
applications
ranging
from
hybrid
nanomaterials
gene‐targeted
therapies.
Considering
the
important
role
POCs,
new
catalytic
approach
for
their
preparation
is
reported
here,
that
could
be
applied
either
on
solid
support
in
anhydrous
media,
post‐synthetically
aqueous
buffer.
Single
amino
acids,
peptides
and
cell
penetrating
(CPPs)
were
conjugated
various
oligo(ribo)nucleotides
with
high
conversions
good
isolated
yields.
The
applicability
method
was
demonstrated
more
than
35
examples
including
an
analogue
commercial
therapeutic
oligonucleotide.
Other
conjugation
partners,
such
as
deoxycholic
acid
biotin
also
successfully
oligonucleotides.
To
highlight
potential
this
approach,
these
conditions
been
iterative
processes,
which
interest
development
DNA‐Encoded
Libraries.
ChemCatChem,
Journal Year:
2023,
Volume and Issue:
15(10)
Published: April 14, 2023
Abstract
Amides
are
one
of
the
most
important
functional
groups
in
organic
chemistry
and
play
essential
roles
both
pharmaceutical
industry
life
sciences.
However,
due
to
natural
reactivity
carboxylic
acids
amines,
their
direct
coupling
is
challenging
often
leads
reactions
that
not
atom‐economic
produce
large
amounts
non‐recoverable
by‐products.
Despite
impressive
number
reagents
available,
sustainable
methods
for
amide
bond
formation
still
needed.
To
address
this
challenge,
a
new
catalytic
approach
preparation
amides
from
amines
reported
here.
This
method
combines
organocatalysis
with
substoichiometric
amount
activating
agent
under
mild
conditions
(open
air,
room
temperature,
green
solvents).
was
applied
good
efficiency
on
wide
range
substrates,
without
epimerization
chiral
stereocenters
SPPS.
Organic Process Research & Development,
Journal Year:
2023,
Volume and Issue:
27(5), P. 982 - 992
Published: May 4, 2023
Diisopropylcarbodiimide
(DIC)
constitutes
one
of
the
most
widely
used
coupling
reagents
for
amide
bond
formation
in
peptide
synthesis.
We
have
previously
reported
that
DIC
contains
a
varying
amount
sulfur
(61–2030
ppm),
and
main
S-containing
impurity
is
thiourea
DITU,
which
exhibits
an
excellent
ability
to
suppress
side
reactions
caused
by
N-oxyl
radicals
formed
from
common
N-hydroxyl-coupling
additives
such
as
HOBt
Oxyma
(Green
Chem.
2019,
21,
5990).
Aiming
understand
how
quality
impacts
synthesis,
here,
we
report
evaluation
14
batches
GMP-grade
seven
different
vendors.
With
elemental
analysis
(S),
gas
chromatography–mass
spectrometry,
high-performance
liquid
chromatography,
chromatography-mass
nuclear
magnetic
resonance,
determined
currently
use
not
but
rather
diazetidine-2-thione
[1,3-diisopropyl-4-(isopropylimino)-1,3-diazetidine-2-thione,
DIDT],
2
+
cycloaddition
between
iPr-NCS.
The
identity
DIDT
was
confirmed
synthesis
iPr-NCS,
followed
spiking
batch
with
synthesized
material.
In
comparative
DITU
aimed
at
determining
their
breakdown
Fmoc-Cys(Trt)-OH
Oxyma,
completely
prevented
Cys
decomposition,
whereas
had
no
effect
on
suppression
amino
acid.
Finally,
catalytic
amounts
well
thiols
DTT
NAC
positive
minimization
HOBt-induced
Fmoc-Trp(Boc)-OH,
urea
DIU,
every
DIC-mediated
reaction,
accelerated
Trp
substrate.
Organic Process Research & Development,
Journal Year:
2023,
Volume and Issue:
27(7), P. 1348 - 1364
Published: June 23, 2023
The
finding
that
the
widely
used
peptide
coupling
reagents
DIC
and
Oxyma
form
toxic
H-CN
(McFarland,
A.
D.
Org.
Process
Res.
Dev.
2019,
23,
2099)
has
prompted
studies
aimed
at
minimization,
attained,
for
example,
by
solvent
engineering
(Erny,
M.
2020,
24,
1341)
substituting
with
TBEC
(Manne,
S.
R.
2022,
26,
2894).
Here,
an
integrated
study
of
TBEC/Oxyma
as
couplers
is
reported,
focusing
not
only
on
performance
in
couplings
but
also
its
cost,
hazards
associated
use,
sustainability
route
synthesis,
end
life
strategies,
well
potential
impact
impurities
reagent
synthesis.
TBEC/Oxyma-mediated
NBP/EtOAc
(1:4)
proceeded
minimal
racemization,
free
precipitation,
radical
side
reactions
irrespective
quality.
These
results
hold
great
promise
broad
adoption
suitable
green
media
a
strategy
sustainable
synthesis
from
R&D
lab
to
manufacturing
plant.
