Ni-Catalyzed Cyanation of (Hetero)Aryl Electrophiles Using the Nontoxic Cyanating Reagent K4[Fe(CN)6]
ACS Catalysis,
Год журнала:
2025,
Номер
15(8), С. 6459 - 6465
Опубликована: Апрель 5, 2025
A
Ni-catalyzed
cyanation
of
aryl
halides
using
potassium
ferrocyanide
(K4[Fe(CN)6])
as
a
nontoxic
cyanide
source
has
been
developed.
Key
features
this
method
include
the
use
biphasic
aqueous
conditions
to
overcome
innate
insolubility
K4[Fe(CN)6]
in
organic
solvents
and
bench-stable
Ni(II)
precatalyst
combined
with
commercially
available
JosiPhos
ligand
that
enhances
practicality
scalability
reaction.
The
inclusion
acidic
additive
tetrabutylammonium
hydrogen
sulfate
was
found
improve
reaction
rate
conversion.
initial
scope
successfully
demonstrated
on
range
(hetero)aryl
bromides,
chlorides,
sulfamates
catalyst
loadings
low
2.5
mol
%.
This
base-metal-catalyzed
methodology
further
translated
decagram
synthesis
pharmaceutical
intermediate,
usurping
prior
Pd-catalyzed
process
employed
hazardous
solvent
pair
(Zn(CN)2,
DMAc).
Язык: Английский
The Catalysis Laboratory at Merck: 20 Years of Catalyzing Innovation
ACS Catalysis,
Год журнала:
2022,
Номер
13(1), С. 475 - 503
Опубликована: Дек. 20, 2022
The
Catalysis
Laboratory
at
Merck
was
established
in
2002
to
discover
and
develop
asymmetric
hydrogenation
transformations
for
application
the
company's
pipeline.
Twenty
years
later,
it
is
safe
say
that
not
only
what
now
feels
like
modest
goal
accomplished,
but
many
varied
catalytic
technologies
have
also
emerged
from
this
group.
Furthermore,
successes
achieved
locally
spawned
an
array
of
further
investments
manifolds
other
enabling
across
industry
academia
alike.
Herein,
we
will
take
a
look
back
team's
humble
origins,
discuss
impacts
been
realized
initial
outlay,
provide
thoughts
on
future
directions
entering
third
decade.
Язык: Английский
Applications of Polymethylhydrosiloxane (PMHS) in Organic Synthesis- Covering up to March 2022
Mini-Reviews in Organic Chemistry,
Год журнала:
2022,
Номер
20(7), С. 708 - 734
Опубликована: Окт. 24, 2022
Abstract:
Based
on
the
type
of
metal
or
non-metal
catalyst
used,
authors
this
paper
have
clearly
highlighted
different
applications
air-stable,
commercially
viable,
and
environmentally
friendly
polymethylhydrosiloxane
(PMHS)
in
organic
synthesis
other
allied
reactions.
The
importance
PMHS
was
emphasised
for
particular
transformation's
success.
In
addition
to
its
wellknown
use
as
a
reducing
agent,
it
has
also
been
demonstrated
variety
applications,
including
ring
cleavage,
cotton
industry,
functional
material
microfluidic
chips,
dehydroaromatization
bio-oils.
article
tries
compile
most
noteworthy
cases
highly
successful
catalysis
over
past
two
decades
so.
Язык: Английский
Nickel-Catalyzed Cyanation of (Hetero)aryl Bromides Using DABAL-Me3 as a Soluble Reductant
Organic Letters,
Год журнала:
2022,
Номер
24(45), С. 8397 - 8400
Опубликована: Ноя. 9, 2022
A
nickel-catalyzed
cyanation
of
(hetero)aryl
halides
using
air-stable
bis(trimethylaluminum)-1,4-diazabicyclo[2.2.2]octane
(DABAL-Me3)
as
a
soluble
reductant
has
been
developed.
The
reaction
uses
readily
available
and
inexpensive
Ni(dppf)Cl2
precatalyst,
substoichiometric
amount
Zn(CN)2,
DABAL-Me3
an
alternative
to
commonly
prescribed
insoluble
reductants.
We
found
the
addition
catalytic
tetrabutylammonium
bromide
(TBABr)
be
beneficial,
due
facilitating
dissolution
low
levels
cyanide
salt
(confirmed
via
control
study).
Similarly,
slow
(TBACN)
solution
is
effective
results
in
completely
homogeneous
mixture.
Язык: Английский
Dehydration of Amides by Redox‐Active Phenalenyl Based Mn‐Catalyst
ChemCatChem,
Год журнала:
2023,
Номер
15(19)
Опубликована: Авг. 8, 2023
Abstract
A
redox‐active
phenalenyl
ligand
coordinated
Mn(III)‐complex
can
be
reduced
chemically
to
generate
an
active
catalyst
containing
a
ligand‐centered
radical.
This
Mn‐catalyst
shows
excellent
catalytic
reactivity
for
silylative
dehydration
of
wide
range
primary
amides
(including
late‐stage
diversification
various
bio‐active
molecules)
synthesize
nitriles
using
inert
and
inexpensive
silane,
polymethylhydrosiloxane
(PMHS),
under
mild
conditions.
Control
experiments
suggest
radical
pathway
the
present
reaction,
initiated
by
Язык: Английский