Abstract
Spirocyclobutyl
oxindoles,
characterized
by
their
unique
three‐dimensional
structures,
are
valuable
building
blocks
for
many
pharmacophores
and
drug
units.
However,
stereoselective
synthetic
strategies
these
scaffolds
remain
underdeveloped,
with
most
existing
methods
relying
on
transition
metal
catalysts
stoichiometric
redox
reagents.
In
this
work,
we
introduce
an
electrochemical
strain‐release
driven
cascade
spirocyclization
of
bicyclo[1.1.0]butane
(BCB)
derivatives
the
synthesis
functionalized
spirocyclobutyl
oxindoles.
Tetrabutylammonium
bromide
serves
a
dual
purpose
as
both
supporting
electrolyte
brominating
agent.
The
method
offers
broad
substrate
scope,
high
atom
economy,
excellent
diastereoselectivity.
stereoselectivity
product
is
controlled
minimizing
dipolar
repulsion
between
amide
C=O
C−Br
bonds.
We
also
explored
methodology′s
versatility
applying
it
to
various
functionalizations
demonstrated
its
scalability
practical
use.
efficient
derivatization
products
allowed
rapid
creation
diverse
library
Hexafluoroisopropanol
(HFIP)-mediated
terminal
selective
heteroarylation
of
allenamides
has
been
accomplished
through
H-bonding
network-enabled
substrate
activation
in
a
robust
fashion.
This
strategy
features
cascade
process
involving
sequential
nucleophilic
addition
followed
by
electrophilic
heteroaromatic
substitution
and
is
well
suited
for
late-stage
functionalization
complex
bioactive
molecules.
The
elucidation
the
underlying
mechanism
was
achieved
comprehensive
combination
several
control
experiments,
kinetic
studies,
isotopic
labeling
isolation
HFIP-allenamide
intermediate
adduct.
Chemical Science,
Год журнала:
2024,
Номер
15(29), С. 11418 - 11427
Опубликована: Янв. 1, 2024
An
environmentally
friendly
electroreduction
approach
is
disclosed
for
site-specific
introduction
of
deuterium
via
anti-Markovnikov
selective
deuteroarylation
alkenes
and
aryl
iodides
with
bipyridine
as
a
mediator
D
2
O
‘D’
source.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(9), С. 1965 - 1971
Опубликована: Март 5, 2024
Abstract
The
first
site‐selective
electrochemical
alkylation
of
tropones
is
realized
by
reacting
2‐acetoxytropones
and
redox‐active‐esters
(RAEs).
electroreductive
protocol
enables
the
preparation
mono‐
disubstituted
in
high
yields
(up
to
71%)
under
very
mild
conditions.
Dedicated
voltammetric
measurements
served
for
identification
as
a
class
valuable
trapping
agents
nucleophilic
radical
species
shed
light
on
whole
mechanistic
profile.
Wide
tolerance
towards
functional
groups
(27
examples)
application
late‐stage
functionalization
bioactive
compound
(
i.
e
.
Colchicine
analogue),
emphasize
synthetic
impact
present
methodology.
Current Research in Green and Sustainable Chemistry,
Год журнала:
2024,
Номер
8, С. 100406 - 100406
Опубликована: Янв. 1, 2024
Atom-economical,
eco-efficient,
metal-
and
chemical
oxidant-free
formation
of
C–C
C–N
bond
from
C(sp2)−H
C(sp3)−H
arenes
toward
the
direct
synthesis
biaryls
anilides
or
N-benzylamides
under
mild
electro-oxidative
conditions
is
described.
The
products
coupling
are
obtained
in
up
to
88%
yields.
Aromatic
substrates
that
oxidized
at
potentials
less
positive
than
+2
V
have
bulky
bromine
iodine
substituents
undergo
homo-coupling
reactions
by
anodic
oxidation
form
dimers.
difficult
oxidize
(Eox
>
V)
preferentially
upon
oxidation.
presence
a
chlorine
substituent
on
aromatic
ring
leads
both
during
electro-oxidation.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(42), С. 28663 - 28668
Опубликована: Окт. 14, 2024
Shono-type
oxidation
to
generate
functionalized
heterocycles
is
a
powerful
method
for
late-stage
diversification
of
relevant
pharmacophores;
however,
development
beyond
oxygen-based
nucleophiles
remains
underdeveloped.
The
limited
scope
can
often
be
ascribed
constant
current
electrolysis
resulting
in
potential
drifts
that
oxidize
desired
nucleophilic
partner.
Herein,
we
report
voltage-controlled
strategy
selectively
broad
substrates,
enabling
modular
C-N
bond
formation
from
protected
amine
nucleophiles.
We
implement
an
electroanalytically
guided
workflow
using
cyclic
voltammetry
(CV)
and
differential
pulse
(DPV)
identify
potentials
across
range
heterocyclic
substrates.
Controlled
(CPE)
generates
α-functionalized
products
moderate
good
yields
carbamate-,
sulfonamide-,
benzamide-derived
importance
voltage
control
further
exemplified
through
systematic
study
comparing
our
developed
CPE
(CCE)
protocols.
Voltage-guided
CCE
traditionally
optimized
reveal
the
maintaining
high
selectivity
over
scope;
case
with
morpholine-derived
substrate
illustrates
negative
impact
drifting
under
CCE.
Sulfonamide
drugs,
which
have
significant
overlap
model
are
rendered
competent
CPE.
Lastly,
sequential
C-O
functionalization
difunctionalized
pyrrolidines
broadening
utility
this
reaction.
The Chemical Record,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 3, 2025
Abstract
Electrocatalysis
is
a
crucial
technology
that
will
enable
future
low‐carbon
chemical
production
and
energy
beyond
fossil
fuels.
Notwithstanding
the
intense
growing
research
in
area,
potentialities
of
field
are
largely
unexplored.
We
provide
case
examples
discuss
emerging
possibilities
have
still
not
been
investigated
enough
but
necessary
to
exploit
this
potential
e‐chemistry.
Starting
from
defining
trends
setting
scene,
as
well
clarifying
difference
between
electrochemistry
electrocatalysis,
some
elements
vision
foster
innovation
discussed.
The
aim
stimulate
discussion
reflection
rather
than
review
state‐of‐the‐art.
Aspects
discussed
regard
i)
passing
electro
photoelectrocatalytic
approaches,
ii)
making
chemicals
air,
iii)
exploitation
both
anodic
cathodic
reactions,
tandem/paired
electrocatalytic
iv)
for
selective
oxidation
mediated
synthesis.
Priorities
strategies
an
e‐chemistry
Intensifying
these
directions
extending
still‐too‐limited
current
including
modelling
design,
effort
accelerate
realisation
distributed
Abstract
Sulfonium
salts
are
typically
bench‐stable
and
readily
available
reagents
that
showcase
diverse
chemical
reactivities.
Owing
to
these
synthetically
valuable
features,
sulfonium
salt
chemistry
has
witnessed
considerable
momentum
over
the
past
decades.
Particularly,
merger
of
electrosynthesis
enabled
utilization
electric
current
in
place
cost‐intensive
hazardous
redox
agents
maximize
attractive
characteristics
salts.
Additionally,
electrochemistry
allowed
chemists
dial
desired
potential,
offering
selective
access
target
products
otherwise
unattainable
by
either
thermal
or
photochemical
manifolds.
These
advantages
led
major
advances
chemistry.
Thus,
we,
herein,
provide
an
overview
early
pioneering
findings
recent
progress
devoted
organic
associated
with
until
December
2024,
aiming
stimulate
future
this
rapidly
evolving
arena.
RSC Advances,
Год журнала:
2025,
Номер
15(19), С. 15302 - 15309
Опубликована: Янв. 1, 2025
Introducing
CF
3
groups
boosts
drug
properties
by
enhancing
metabolic
stability
and
bioavailability.
This
study
reports
an
electrochemical
oxidative
difunctionalization
of
flexible
alkenes
to
form
-substituted
lactones
cyclic
ethers.
