Organic Process Research & Development,
Journal Year:
2020,
Volume and Issue:
24(11), P. 2665 - 2675
Published: Sept. 4, 2020
Solvents
constitute
the
largest
component
for
many
chemical
processes
and
substitution
of
nonrenewable
solvents
is
a
longstanding
goal
green
chemistry.
Here,
we
show
that
Pd-catalyzed
carbonylative
couplings,
such
as
cross-couplings,
aminocarbonylations,
alkoxycarbonylations,
can
be
successfully
realized
using
renewable
solvents.
The
present
research
covers
not
only
well-established
solvents,
2-methyltetrahydrofuran
(2MeTHF),
limonene,
dimethyl
carbonate,
but
also
recently
introduced
biomass-derived
1,1-diethoxyethane,
isosorbide
ether,
eucalyptol,
rose
oxide,
γ-terpinene,
α-pinene.
coupling
boronic
acids
aryl
bromides
works
well
in
limonene.
Aminocarbonylation
gave
excellent
results
α-pinene,
while
alkoxycarbonylation
was
successful
2MeTHF,
carbonate.
developed
methods
based
on
used
synthesis
commercial
drug
Trimetozine
an
analogue
Itopride.
Organic Letters,
Journal Year:
2019,
Volume and Issue:
21(16), P. 6534 - 6538
Published: July 31, 2019
An
efficient
electro-oxidative
C–H/N–H
activation
with
1,3-diynes
has
been
achieved
a
robust
earth-abundant
cobalt
catalyst.
The
electrochemical
C–H
functionalization
was
accomplished
ample
scope
and
remarkable
functional
group
compatibility
in
simple
undivided
cell.
This
protocol
avoids
the
utilization
of
stoichiometric
cost-intensive
chemical
oxidants
activation,
thus
forming
hydrogen
as
only
byproduct.
Green Chemistry,
Journal Year:
2020,
Volume and Issue:
22(18), P. 5937 - 5955
Published: Jan. 1, 2020
This
review
summarizes
the
adoption
of
flow
technology
for
synthesis
a
variety
APIs
in
period
2015–2020.
A
major
attention
has
been
dedicated
to
compare
batch
and
procedures
by
also
comparing
their
sustainability.
Chemical Communications,
Journal Year:
2021,
Volume and Issue:
57(83), P. 10827 - 10841
Published: Jan. 1, 2021
Over
the
last
decade,
high-valent
cobalt
catalysis
has
earned
a
place
in
spotlight
as
valuable
tool
for
C-H
activation
and
functionalization.
Since
discovery
of
its
unique
reactivity,
more
attention
been
directed
towards
utilization
an
alternative
to
noble
metal
catalysts.
In
particular,
Cp*Co(III)
complexes,
well
simple
Co(II)
Co(III)
salts
combination
with
bidentate
chelation
assistance,
have
extensively
used
development
novel
transformations.
this
review,
we
demonstrated
existing
trends
functionalization
methodology
using
highlighted
main
challenges
overcome,
perspective
directions,
which
need
be
further
developed
future.
ACS Sustainable Chemistry & Engineering,
Journal Year:
2021,
Volume and Issue:
9(29), P. 9508 - 9540
Published: July 12, 2021
Flow
chemistry
has
changed
chemical
process
designs
toward
intensification
and
is
generally
considered
as
green
methodology.
In
this
connection,
perspective
provides
a
more
critical
holistic
view
about
the
sustainability
of
flow
by
introducing
both
simple
complex
tools
for
environmental
quantitative
assessment
on
providing
examples
how
they
were
used
chemistry.
The
latter
also
shows
what
can
add
to
make
processes
sustainable.
With
increasing
complexity
assessment,
metrics,
life
cycle
methodology,
circular
transition
indicators
are
discussed.
way,
assessed
first
level
reaction
only
then
moving
beyond.
chemists
very
aware
principles
their
metrics.
Yet,
hardly
use
circularity
analysis
not
been
made.
When
those
assessments
used,
it
usually
done
researchers
with
an
ecology
background.
This
aims
opportunities
that
provide
protecting
our
planet
requires
consideration.
critically
states
each
three
types
do
limitations
are.
ACS Sustainable Chemistry & Engineering,
Journal Year:
2020,
Volume and Issue:
8(46), P. 17154 - 17164
Published: Nov. 11, 2020
Zirconium
based
metal–organic
framework
UiO-66
is
to
date
considered
one
of
the
benchmark
compounds
among
stable
MOFs,
and
it
has
attracted
huge
attention
for
its
employment
in
many
strategic
applications.
Large
scale
production
industrial
purposes
requires
use
safe
green
solvents,
fulfilling
chemistry
principles
able
replace
N,N-dimethylformamide
(DMF),
which,
despite
toxicity,
still
most
efficient
solvent
obtaining
high
quality.
Herein
we
report
on
a
survey
about
40
different
solvents
with
polarities,
boiling
points
acidities,
used
laboratory
synthesis
quality
crystals.
The
were
chosen
according
European
REACH
Regulation
1907/2006
those
having
low
cost
toxicity
being
fully
biodegradable.
Concerning
MOF
synthesis,
relevant
parameters
establishing
results
obtained
are
degree
crystallinity,
microporosity,
specific
surface
area,
yield,
recyclability.
Taking
into
account
also
chemical
physical
properties
all
color
code
was
assigned
order
give
final
assessment
synthesis.
Defectivity
products,
acidic
modulators,
alternative
Zr
salts
have
been
taken
consideration.
Preliminary
lead
conclusion
that
GVL
(γ-valerolactone)
promising
replacing
DMF
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(11), P. 6457 - 6462
Published: May 12, 2020
Versatile
and
robust
cobalt
catalysis
enabled
the
electrochemical
C–H
allylation
with
nonactivated
alkenes.
In
contrast
to
precious
palladium,
rhodium,
iridium,
ruthenium
catalysts
that
are
limited
electronically
activated
styrenes
acrylates,
we
herein
disclose
cobalt-catalyzed
electro-oxidative
allylations
Thus,
allylated
benzamides
were
obtained
high
levels
of
chemoselectivity,
positional
selectivity,
regioselectivity
in
biomass-derived
solvent
γ-valerolactone.
Detailed
mechanistic
studies
provided
strong
support
for
a
base-assisted
internal
electrophilic-type
substitution
mechanism
key
activation
step.
The
cobaltaelectro-catalysis
overall
achieved
resource-economy
by
avoiding
use
stoichiometric
chemical
oxidants,
H2
as
only
byproduct.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(30), P. 13102 - 13111
Published: June 13, 2020
The
iron-catalyzed
hydroarylation
of
allenes
was
accomplished
by
weak
phenone
assistance.
C-H
activation
proceeded
with
excellent
efficacy
and
high
ortho-regioselectivity
in
proximity
to
the
weakly
coordinating
carbonyl
group
for
a
range
substituted
phenones
allenes.
Detailed
mechanistic
studies,
including
isolation
key
intermediates,
structural
characterization
an
iron-metallacycle,
kinetic
analysis,
allowed
sound
elucidation
plausible
catalytic
working
mode.
This
rationale
is
supported
detailed
computational
density
functional
theory
which
fully
address
multi-spin-state
reactivity.
Furthermore,
operando
nuclear
magnetic
resonance
monitoring
reaction
provided
insights
into
mode
action
alkylation
Chemistry - A European Journal,
Journal Year:
2019,
Volume and Issue:
25(71), P. 16382 - 16389
Published: Oct. 28, 2019
Despite
major
advances,
organometallic
C-H
transformations
are
dominated
by
precious
5d
and
4d
transition
metals,
such
as
iridium,
palladium
rhodium.
In
contrast,
the
unique
potential
of
less
toxic
Earth-abundant
3d
metals
has
been
underexplored.
While
iron
is
most
naturally
abundant
metal,
its
use
in
oxidative,
activation
faced
limitations
due
to
need
for
superstoichiometric
amounts
corrosive,
cost-intensive
DCIB
sacrificial
oxidant.
To
fully
address
these
restrictions,
we
describe
herein
unprecedented
merger
electrosynthesis
with
iron-catalyzed
through
oxidation-induced
reductive
elimination.
Thus,
ferra-
manganaelectro-catalyzed
arylations
were
accomplished
at
mild
reaction
temperatures
ample
scope
action
sustainable
catalysts,
employing
electricity
a
benign