Angewandte Chemie,
Год журнала:
2024,
Номер
136(31)
Опубликована: Май 16, 2024
Abstract
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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(31)
Опубликована: Май 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 Chemistry Frontiers,
Год журнала:
2024,
Номер
11(15), С. 4318 - 4342
Опубликована: Янв. 1, 2024
This
review
primarily
focuses
on
the
generation
of
aryl
radicals
via
an
electroreduction
strategy,
and
systematically
elaborates
synthetic
applications,
scope,
limitations
substrates.
Abstract
Recently,
electrochemical
methods
have
been
harnessed
as
a
transition
metal‐free
strategy
for
borylation
reactions
in
the
synthesis
of
organoboron
compounds.
This
article
reviews
C−C
and
C−Het
bonds,
offering
systematic
discussion
C−C,
C−N,
C−O,
C−S
bond
reactions.
These
transformations
are
applied
to
substrates
including
ammonium
salts,
aryl
azo
sulfones,
carboxylic
acids,
arylhydrazines,
nitroarenes,
alcohols,
thioethers,
showcasing
broad
compatibility.
Additionally,
review
discusses
reaction
mechanisms,
scalability,
practical
applications
these
strategies.
The
concludes
by
outlining
future
research
directions
reactions,
aiming
at
expending
their
incorporating
boron
into
wider
array
organic
compounds,
challenging
unactivated
C−F
borylations.
Abstract
In
2014,
the
World
Health
Organization
called
drug
resistance
to
antibiotics
a
“major
global
threat”.
Therefore,
ever‐increasing
human
need
for
new
with
greater
effectiveness
and
fewer
side
effects
is
necessity.
Meanwhile,
sulfonamides
are
among
most
widely
used
in
world.
this
review,
attention
has
been
paid
key
points
raised
various
papers
field
of
electrosynthesis
these
compounds,
considering
their
positive
negative
aspects,
including
interaction
as
much
possible
principles
green
chemistry
absence
environmental
risks,
low
cost
versatility
scalability
method
along
acceptable
efficiency.
following,
we
will
discuss
research
focused
on
synthesis
sulfonamide
derivatives
based
oxidation
or
reduction
compounds
which
take
place
working
electrode
surface.
The
hydrofunctionalizations
of
readily
available
alkenes
and
alkynes
are
one
the
most
effective
useful
routes
to
afford
diverse
value-added
compounds.
Although
traditional
hydrofunctionalization
strategies
catalyzed
by
metal
catalysts
present
convenient
approaches,
they
also
accompanied
resource
consumption
environmental
crisis.
Electrosynthesis,
as
a
renewable
sustainable
technology,
has
become
cost-
atom-efficient
synthetic
route.
In
this
review,
electrochemical-induced
summarized
presented.
each
section,
electrochemical
strategy
access
hydrogenation
other
(hydroboration,
hydrosilylation,
hydroalkylation,
hydroalkoxylation,
hydrocyanation,
hydrocarboxylation,
etc.
)
products
elaborated
in
detail
separately.
Finally,
current
challenges
prospects
for
unsaturated
carbon‒carbon
(C‒C)
bonds
discussed
briefly.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(28)
Опубликована: Май 20, 2024
Abstract
In
recent
years,
the
functionalization
of
1,3‐butadiene
has
become
an
attractive
strategy
for
constructing
allyl
compounds
with
molecular
and
structural
complexity,
current
research
focuses
on
synthetic
chemistry
organic
synthesis.
Compared
traditional
synthesis
method,
methods
promoted
by
photochemistry
or
electrochemistry
represent
environmentally
friendly
mild
strategy.
this
review,
reactions
under
photochemical/electrochemical
processes
in
years
are
reviewed
according
to
classification
systems,
particular
emphasis
corresponding
reaction
mechanism,
which
lays
a
foundation
further
exploration
new
catalytic
methods.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(18), С. 5306 - 5324
Опубликована: Янв. 1, 2024
This
review
summarizes
recent
achievements
in
electrosynthesis
of
organohalides
through
difunctionalization
alkenes
and
alkynes
provides
insights
into
future
directions
for
the
development
field.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(21), С. 15151 - 15158
Опубликована: Окт. 18, 2023
NHC-boranes
have
been
treated
as
a
reliable
source
of
boryl
radicals.
In
this
study,
regioselective
hydroborylation
ketene
dithioacetals
with
NHC-borane
was
achieved
under
mild
conditions
via
visible-light-promoted
radical
chain
process
using
thiophenol
proton
donor
and
hydrogen
atom
transfer.
This
protocol
features
low-cost
catalyst,
good
functional
group
tolerance,
relatively
broad
range
substrate
scope,
to
excellent
yields.
Moreover,
mechanism
reaction
preliminarily
studied.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(20), С. 5985 - 6003
Опубликована: Янв. 1, 2024
This
review
summarizes
recent
advances
in
alkynyl
trifluoroborate
chemistry,
emphasizing
their
unique
reactivity
and
stability
organic
synthesis
biological
applications
under
transition
metal
catalyst-free
conditions.
