Oxidative
coupling
of
2-naphthols
to
1,1'-bi-2-naphthols
in
air
at
50
°C
was
conducted
by
using
VOx
supported
on
metal
oxides
prepared
flame
spray
pyrolysis.
Among
the
tested
catalysts,
highest
yield
(91%)
achieved
VOx/t-ZrO2
(containing
7.8
wt%
as
V2O5).
The
catalytic
activity
decreased
content
increased.
At
lower
content,
catalyst
primarily
consisted
monovanadate
species
with
square
pyramidal
coordination.
As
increased,
fraction
monovanadates
decreased,
whereas
that
polyvanadates
H2
temperature-programmed
reduction
measurements
revealed
exhibited
temperatures
than
polyvanadates.
Therefore,
our
results
suggest
highly
reactive
t-ZrO2
are
active
sites
for
reaction.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(5), С. 3043 - 3051
Опубликована: Янв. 26, 2024
Cross-electrophile
coupling
has
emerged
as
an
attractive
and
efficient
method
for
the
synthesis
of
C(sp2)–C(sp3)
bonds.
These
reactions
are
most
often
catalyzed
by
nickel
complexes
nitrogenous
ligands,
especially
2,2′-bipyridines.
Precise
prediction,
selection,
design
optimal
ligands
remains
challenging,
despite
significant
increases
in
reaction
scope
mechanistic
understanding.
Molecular
parameterization
statistical
modeling
provide
a
path
to
development
improved
bipyridine
that
will
enhance
selectivity
existing
broaden
electrophiles
can
be
coupled.
Herein,
we
describe
generation
computational
ligand
library,
correlation
observed
outcomes
with
features
silico
Ni-catalyzed
cross-electrophile
coupling.
The
new
nitrogen-substituted
display
5-fold
increase
product
formation
versus
homodimerization
when
compared
current
state
art.
This
yield
was
general
several
couplings,
including
challenging
aryl
chloride
N-alkylpyridinium
salt.
ACS Sustainable Chemistry & Engineering,
Год журнала:
2023,
Номер
11(28), С. 10545 - 10554
Опубликована: Июль 7, 2023
Bayesian
optimization
is
a
powerful
machine
learning
technique
that
particularly
well-suited
for
optimizing
chemical
reactions
in
the
early
stages
of
process
development.
It
can
efficiently
explore
vast
reaction
spaces
and
predict
high-yielding
conditions
by
evaluating
only
small
number
experiments.
In
this
report,
we
investigated
potential
as
tool
to
enhance
sustainability
synthesis.
Specifically,
focused
on
real-world
early-stage
development
example:
C–N
coupling
sterically
encumbered
bromo-pyrazines
with
amines.
Our
objective
was
identify
sustainable
utilize
Earth-abundant
copper
catalysts
non-hazardous
solvents.
We
used
optimizers
various
acquisition
functions.
assessed
their
performance
identified
key
features
affecting
results.
The
optimized
enabled
synthesis
range
pyrazines
pyridines
moderate
excellent
yields.
Chemical Science,
Год журнала:
2024,
Номер
15(24), С. 9016 - 9025
Опубликована: Янв. 1, 2024
Initial
calculations
of
environmental
footprints
associated
with
using
Ni
vs
Pd
catalysis
in
a
representative
metal-catalyzed
Suzuki–Miyaura
cross-coupling
reveal
that
the
choice
ligated
metal
is
often
NOT
consequence.
Rather,
it
culmination
other
parameters
such
as
medium.
Organic Process Research & Development,
Год журнала:
2023,
Номер
27(5), С. 831 - 846
Опубликована: Май 3, 2023
From
a
careful
analysis
of
the
recent
literature,
it
seems
clear
that
many
transition-metal-catalyzed
processes
used
in
API
synthesis
are
developed
without
resorting
to
any
kind
kinetic
analysis.
Even
acknowledging
some
these
were
for
early
development
projects
and
did
not
need
be
thoroughly
optimized,
lack
work
is
surprising.
This
Perspective
suggests
that,
addition
utilization
modern
technologies
such
as
high-throughput
experimentation
(HTE)
classical
optimization
tools
Design
Experiments
(DOE),
modest
level
necessary
develop
truly
effective
catalytic
reactions.
We
offer
basic
theoretical
considerations
suggest
rather
simple
which
can
employed
integrate
steps
into
development.
Substitution
of
one
metal
catalyst
for
another
is
not
straightforward
as
simply
justifying
this
change
based
on
the
availability
and/or
cost
metals.
A
life
cycle-like
assessment
was
performed
leading
to
conclusion
that
commonly
held
view
use
earth-abundant
metals
(and
in
case
study,
Ni)
are
replacements
palladium
most
notably
cross
coupling
reactions,
and
Suzuki-Miyaura
couplings,
particular,
an
incomplete
analysis
entire
picture.
This
notion
can
be
misleading,
unfortunately
derives
nowadays
mainly
from
standpoint
cost,
some
degree,
relative
natural
abundance
mining
impact
each
metal.
However,
a
more
realistic
appreciation
emerges
when
several
additional
reaction
parameters
involved
couplings
considered.
Such
unequivocally
points
major
climate
brought
about
by
organic
solvents,
while
actually
play
subordinate
roles
terms
CO2-release
into
environment.
Clearly,
study
reveals
factors
contribute
various
ways
overall
carbon
footprint.
Hence,
far
detailed
required
than
typically
being
utilized!
Cell Reports Physical Science,
Год журнала:
2023,
Номер
4(9), С. 101548 - 101548
Опубликована: Авг. 21, 2023
This
perspective
provides
an
entry-level
conversation
concerning
base
metal
catalysis
as
a
green
and
sustainable
solution
in
industrial
academic
contexts.
We
establish
definition
of
"base
metal,"
challenging
readers
to
consider
the
ethical
implications
sourcing.
explore
what
it
means
be
"sustainable"
provide
information
on
current
efforts
synthetic
chemistry.
examples
catalytic
trends
transformations
popular
fields
such
cross-coupling
small-molecule
conversion,
highlighting
relevant
systems.
Finally,
we
social
context—for
example,
decisions
related
catalyst
development
are
often
driven
by
factors
including
costliness,
safety,
adoptability
(whether
society
will
accept
its
usage),
performance.
How
do
move
forefront?
Is
concerned
if
materials
fabricated
from
cheaper
more
abundant
sources?
does
chemistry
community
guide
this
knowledge
translation?
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
We
report
a
nickel-catalyzed
cascade
reaction
leading
to
the
arylation
of
an
alkyne-induced
acyl
migration
and
formation
all-carbon
tetra-substituted
alkenes
in
good
yields
with
exclusive
Z
-selectivity.
Organic Process Research & Development,
Год журнала:
2023,
Номер
27(9), С. 1667 - 1676
Опубликована: Сен. 6, 2023
Solvents
used
to
run
chemical
reactions
on
a
process
scale
are
the
largest
contributors
hazardous
waste
in
active
pharmaceutical
ingredient
(API)
manufacturing.
Frequently,
solvents
providing
optimal
reaction
performance
toxic
and
environmentally
damaging.
The
rapid
emergence
of
mechanochemistry
as
practical
tool
for
organic
synthesis
has
piqued
interest
chemists
potential
method
that
could
reduce
solvent
use
perform
transformations
safer
friendly
manner.
Reactive
extrusion
become
viable
option
multigram-scale
continuous
Herein,
we
demonstrate
small-scale
ball-milling
experiments
screening
optimizing
system
allow
translation
Sonogashira
coupling
from
twin-screw
implementation
at
larger
scale.
Chemical Communications,
Год журнала:
2024,
Номер
60(28), С. 3826 - 3829
Опубликована: Янв. 1, 2024
The
development
of
an
electrochemical
cobalt
catalyzed
C–Cl
bond
activation
at
room
temperature
for
the
nucleophilic
addition
aryl
and
vinyl
chlorides
to
α-ketoamides
extension
enantioselective
reaction
is
described.
