Chemistry - An Asian Journal,
Journal Year:
2024,
Volume and Issue:
19(9)
Published: March 16, 2024
A
benign
electrochemical
method
to
access
6-methylphenanthridines
from
2-isocyanobiaryls
using
N,N-dimethylformamide
(DMF)
as
a
methyl
source
is
reported.
The
protocol
operates
at
ambient
temperature
without
the
need
for
harmful
methylating
reagents.
Mechanistic
studies
suggested
that
DMF
delivered
methylene
synthon,
followed
by
reduction
cathode
and
tautomerization.
offers
environmental
benefits
avoiding
metal-based
reagents
harsh
conditions.
Organic Process Research & Development,
Journal Year:
2024,
Volume and Issue:
28(2), P. 338 - 366
Published: Jan. 18, 2024
This
review
summarizes
examples
of
organic
electrosynthesis
from
the
peer-reviewed
literature
2000
to
2023
that
have
been
conducted
on
scales
20
g
or
above.
A
significant
portion
these
were
a
≤100
scale,
while
detailed
reports
kilogram-scale
remain
scarce
in
pharmaceutical
industry.
In
addition
chemical
transformation,
this
also
highlights
type
reactor
used
and
projected
productivity
metric
as
ways
compare
different
reports.
The
selected
scale-ups
described
herein
illustrate
remaining
challenges
currently
preventing
routine
use
large-scale
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(16)
Published: Feb. 14, 2024
C-C
linked
glutarimide-containing
structures
with
direct
utility
in
the
preparation
of
cereblon-based
degraders
(PROTACs,
CELMoDs)
can
be
assessed
a
single
step
from
inexpensive,
commercial
α-bromoglutarimide
through
unique
Brønsted-acid
assisted
Ni-electrocatalytic
approach.
The
reaction
tolerates
broad
array
functional
groups
that
are
historically
problematic
and
applied
to
simplified
synthesis
dozens
known
compounds
have
only
been
procured
laborious,
wasteful,
multi-step
sequences.
is
scalable
both
batch
flow
features
trivial
procedure
wherein
most
time-consuming
aspect
setup
weighing
out
starting
materials.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(31)
Published: May 16, 2024
Aryl
radicals
play
a
pivotal
role
as
reactive
intermediates
in
chemical
synthesis,
commonly
arising
from
aryl
halides
and
diazo
compounds.
Expanding
the
repertoire
of
sources
for
radical
generation
to
include
abundant
stable
organoboron
reagents
would
significantly
advance
chemistry
broaden
their
reactivity
profile.
While
traditional
approaches
utilize
stoichiometric
oxidants
or
photocatalysis
generate
these
reagents,
electrochemical
conditions
have
been
largely
underexplored.
Through
rigorous
mechanistic
investigations,
we
identified
fundamental
challenges
hindering
generation.
In
addition
high
oxidation
potentials
aromatic
compounds,
electrode
passivation
through
grafting,
homocoupling
radicals,
decomposition
issues
were
identified.
We
demonstrate
that
pulsed
electrosynthesis
enables
selective
efficient
by
mitigating
challenges.
Our
discoveries
facilitated
development
first
conversion
potassium
trifluoroborate
salts
into
C-P
bonds.
This
sustainable
straightforward
oxidative
approach
exhibited
broad
substrate
scope,
accommodating
various
heterocycles
chlorides,
typical
substrates
transition-metal
catalyzed
cross-coupling
reactions.
Furthermore,
extended
this
methodology
form
C-Se,
C-Te,
C-S
bonds,
showcasing
its
versatility
potential
bond
formation
processes.
Organic Process Research & Development,
Journal Year:
2024,
Volume and Issue:
28(5), P. 1877 - 1885
Published: March 1, 2024
The
burgeoning
interest
in
new
electrochemical
methods
holds
promise
to
provide
a
plethora
of
strategic
disconnections
for
pharmaceutical
compounds
that
are
safer,
less
wasteful,
and
more
streamlined
than
traditional
chemical
strategies.
use
organic
electrochemistry
the
commercial
production
pharmaceuticals
is
exceedingly
rare
due
lack
modular
infrastructure.
Herein
we
describe
cascading
continuous
stirred
tank
reactors
with
individual
cell
potential
control
applied
over
reaction
"stages"
which
demonstrate
balance
between
high
selectivity
throughput
necessary
be
viable
strategy
space.
Using
degree
afforded
by
this
reactor
design,
1
kg
demonstration
was
achieved
9
h
yield
(2.6
kg/day
throughput).
Organic Process Research & Development,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 7, 2025
A
scalable
electrochemical
process
to
synthesize
iminophosphorane
ligands
is
reported.
The
application
of
these
iminophosphoranes
was
recently
reported
in
Ni-catalyzed
cross-electrophile
and
C–N
cross-couplings.
use
parallel
plate
flow
reactors
enables
the
synthesis
on
a
multigram
scale,
with
selected
examples
up
0.6
kg
scale.
Direct
crystallization
from
end
reaction
mixture
for
provides
facile
isolation
processes.
This
article
also
details
improvements
our
capabilities
across
scales,
including
addressing
material
compatibility
issues,
increasing
accessible
range
rates,
integration
analytical
technology
tools.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(19)
Published: Feb. 15, 2024
Abstract
The
first
total
synthesis
of
dragocins
A−C,
remarkable
natural
products
containing
an
unusual
C4’
oxidized
ribose
architecture
bridged
by
a
polyhydroxylated
pyrrolidine,
is
presented
through
route
featuring
number
uncommon
maneuvers.
Several
generations
towards
the
target
molecules
are
presented,
including
spectacular
failure
key
C−H
oxidation
on
late‐stage
intermediate.
final
features
rapid,
stereocontrolled
access
to
densely
functionalized
pyrrolidine
and
unprecedented
diastereoselective
oxidative
electrochemical
cyclization
forge
hallmark
9‐membered
ring.
Preliminary
studies
suggest
this
protocol
generally
useful.
