Dearomative 1,4-Difunctionalization of Non-Activated Arenes Enabled by Boryl Radical-Mediated Halogen-Atom Transfer
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 1294 - 1304
Опубликована: Янв. 7, 2025
Given
the
widespread
presence
of
spirocyclic
scaffolds
in
natural
products
and
pharmacologically
relevant
synthetic
compounds,
development
efficient
methodologies
for
their
construction
holds
great
importance
medicinal
chemistry
pharmaceutical
research.
In
this
study,
a
general
photochemical
dearomative
spirocyclization
nonactivated
arenes
has
been
established.
The
key
to
method
lies
ability
amine-borane
radicals
activate
aryl
bromides
iodides
via
halogen-atom
transfer,
thereby
allowing
conversion
halides
into
corresponding
subsequent
chemodivergent
transformations.
remarkable
compatibility
versatility
1,4-difunctionalization
is
showed
by
rapid
assembly
structurally
diverse
1,4-cyclohexadiene-based
spirocycles
incorporating
oxindole,
indoline,
or
dihydrobenzofuran
subunits.
Moreover,
potential
utility
protocol
exemplified
formal
total
synthesis
vasopressin
V2
receptor
antagonist
Satavaptan.
Язык: Английский
Electrochemical umpolung of C‐H nucleophiles bearing three electron‐withdrawing groups to trigger radical 1,2‐alkylarylations of allylic alcohols
Advanced Synthesis & Catalysis,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 31, 2025
Abstract
The
electrochemical
catalyst‐free
generation
of
carbon
radicals
bearing
three
electron‐withdrawing
groups
from
the
corresponding
C−H
nucleophiles
remains
unexplored.
To
this
end,
we
report
a
direct
electro‐oxidation
strategy
to
access
these
electrophilic
under
conditions.
Enabled
by
strategy,
radical
1,2‐alkylarylations
allylic
alcohols
was
realized,
affording
β
‐quaternary
ketones
with
high
functional
group
compatibility.
This
protocol
is
operationally
simple
and
also
easy
scale
up.
Язык: Английский
The Electrosynthesis of Highly Encumbered Biaryls from Aryl o-Iodobenzyl Ethers by a Radical to Polar Crossover Sequence.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Highly
encumbered
2,2',6-tri-
and
2,2',6,6'-tetra-substituted
biaryls
are
readily
prepared
from
aryl
ortho-iodobenzyl
ethers
through
mediated
cathodic
reduction
under
flow.
The
reaction
proceeds
via
the
stepwise
transfer
of
two
electrons:
first
to
induce
loss
iodide
a
radical
cyclisation,
second
polar
fragmentation.
Язык: Английский
Electrosynthesis of 1,4-diene derivatives bearing cyclopentene skeleton
Yaqi Qiao,
Xiaoqing Fan,
Chengcheng Yuan
и другие.
iScience,
Год журнала:
2025,
Номер
28(3), С. 111976 - 111976
Опубликована: Фев. 10, 2025
1,n-Dual
Π
systems
including
1,4-diene
derivatives
have
been
widely
used
as
the
elegant
radical
receptors
to
promote
cascade
additions
give
highly
functionalized
polycyclic
scaffolds.
However,
tedious
and
complicated
preparation
of
former
deters
broad
utilization
compromises
practical
value.
Herein,
a
straightforward
was
developed
from
easily
accessible
alkynes
γ,δ-unsaturated
carboxylic
acids
via
electrochemical
oxidation
cyclization
Hofmann
elimination.
This
transformation
features
with
good
excellent
yields,
functional
group
compatibility,
selectivity
without
any
Zaitsev
elimination
product
detected.
Язык: Английский
Electrochemical Preparation and Transformation of Sulfonium Salts
ChemElectroChem,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 5, 2025
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.
Язык: Английский
Electrochemically induced Meerwein arylation as a green strategy for the synthesis of arylbenzoquinone derivatives under batch and flow conditions
Research Square (Research Square),
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 10, 2025
Abstract
An
electrochemical
Meerwein
arylation
reaction
was
reported
for
the
synthesis
of
aryl-benzoquinone
derivatives.
In
this
work,
efficient
derivatives
by
direct
electrolysis
aqueous
solution
containing
hydroquinone
and
aryldiazonium
salts
in
batch
a
homemade
continuous-flow
cells
is
reported.
system,
products
were
obtained
simple
undivided
cell
equipped
with
copper
anode
stainless
steel
cathode.
continuous
flow
simply
passing
salt
through
tube
made
rod
center.
All
equipment
required
both
types
from
common
commercial
sources.
This
protocol
green
cost-effective
due
to
use
electricity
performed
under
mild
safe
conditions
without
toxic
solvents
catalysts.
Язык: Английский
Electrochemical Deaminative Carboxylation of Aryltriazenes with CO2 to Aryl Carboxylic Acids
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 18, 2025
The
utilization
of
CO2
as
an
appealing
chemical
feedstock
for
diverse
synthetically
valuable
products
is
constantly
evolving,
potentially
alleviating
production
that
relies
on
petrochemistry.
Herein
we
report
the
first
example
electrochemical
deaminative
carboxylation
aryltriazenes
with
CO2.
reaction
can
be
performed
under
mild
and
catalyst-free
conditions
by
using
sustainable
methods
a
green
C1
building
block,
efficiently
converting
range
readily
available
into
carboxylic
acids.
In
particular,
formation
C-C
bonds
would
impactful
addition
to
synthesis
toolbox.
Язык: Английский
Alkylthiolation of Aryl Halides under Electrochemical Conditions
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 25, 2024
An
electrochemical
protocol
for
the
alkylthiolation
of
aryl
halides
was
developed.
By
using
dialkyl
disulfides
as
alkylthio
sources,
Mg
plate
sacrificial
anode
and
graphite
felt
(GF)
cathode,
a
series
sulfides
were
obtained
in
moderate
to
good
yields.
The
approach
also
suitable
synthesis
selenides.
This
method
has
features
such
simple
reaction
conditions
functional
group
compatibility,
which
makes
it
have
application
prospect
organic
drug
synthesis.
Язык: Английский