Traditional
etherification
methods,
although
staples
in
synthetic
chemistry,
often
fall
short
the
efficient
construction
of
sterically
hindered
dialkyl
ethers,
especially
under
mild
and
practical
conditions.
Recent
advances
have
attempted
to
address
these
limitations,
typically
relying
on
transition
metal
catalysts,
external
reductants,
or
harsh
reaction
In
this
work,
we
disclose
a
novel
electrochemical
approach
that
enables
synthesis
ethers
from
economically
relevant
readily
accessible
alcohols
without
need
for
sacrificial
oxidants.
Our
protocol
exploits
conditions
generate
reactive
carbocations,
which
are
subsequently
captured
by
alcohol
nucleophiles
yield
desired
ethers.
This
method
is
cost-effective,
practical,
broad
scope,
providing
valuable
addition
chemists'
toolkit
ether
synthesis.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(31), С. 21257 - 21263
Опубликована: Июль 26, 2024
Because
of
their
robustness
and
orthogonal
reactivity
features,
alkyl
germanes
bear
significant
potential
as
functional
handles
for
the
construction
C(sp3)-rich
scaffolds,
especially
in
context
modular
synthetic
approaches.
However,
to
date,
only
radical-based
has
been
accessible
from
these
handles,
which
limits
types
possible
decorations.
Here,
we
describe
first
general
C(sp3)–heteroatom
bond
formation
(−GeEt3)
by
leveraging
electrochemistry
unlock
polar
reactivity.
This
approach
allowed
us
couple
C(sp3)–GeEt3
with
a
variety
nucleophiles
construct
ethers,
esters,
amines,
amides,
sulfonamides,
sulfides,
well
C–P,
C–F,
C–C
bonds.
The
compatibility
electrochemical
strategy
C1
motif
was
also
showcased,
involving
sequential
functionalization
Cl,
Bpin,
ultimately
GeEt3
via
electrochemistry.
A
novel
electrochemical
approach
for
the
synthesis
of
hindered
alkyl
fluorides
has
been
developed.
The
protocol
grants
access
to
a
diverse
array
tertiary
and
secondary
using
readily
attainable
organoboron
precursors
under
mild
conditions.
efficiency
system
stems
from
dual
activation
redox-active
borate
intermediate,
providing
both
electrophilic
nucleophilic
reaction
partners
in
form
an
internally
generated
ion
pair.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(44)
Опубликована: Июль 30, 2024
Abstract
This
Minireview
examines
a
selection
of
case
studies
that
showcase
distinctive
and
enabling
electrochemical
approaches
have
allowed
for
the
generation
reaction
carbocation
intermediates
under
mild
conditions.
Particular
emphasis
is
placed
on
progress
has
been
made
in
this
area
organic
synthesis
polymer
chemistry
over
past
decade.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 12, 2024
Electrochemical
reactions
via
carbocation
intermediates
remain
fundamental
transformations
that
build
up
molecular
functionality
and
complexity
in
a
sustainable
manner.
Enantioselective
control
of
such
processes
is
great
challenge
highly
ionic
electrolyte
solution.
Here,
we
report
an
anodic
generation
chiral
α-imino
by
enamine
catalysis.
The
can
be
intercepted
variety
nucleophiles
as
alcohols,
water
thiols
with
high
stereoselectivity.
key
SN1
step
proceeds
tertiary
amine-mediated
proton
shuttle
facilitates
facial
selection
reacting
carbocation.
Carbocations
are
useful
synthetic
which
enable
direct
functionalization
carbon
centers,
but
their
manner
uses
mild
conditions
enables
stereoselective
interception
remains
longstanding
goal
organic
chemists.
the
authors
use
electrochemical
oxidation
to
synthesize
scaffolds
from
racemic
α-branched
aldehydes.
Organic Letters,
Год журнала:
2023,
Номер
26(1), С. 198 - 203
Опубликована: Дек. 28, 2023
A
practical
method
for
C(sp3)–B
bond
activation
was
developed.
Using
a
combination
of
alkyl
trifluoroborates
and
N-iodosuccinimide
(NIS),
various
C(sp3)–heteroatom
bonds
were
readily
generated
in
an
efficient
manner.
Mechanistic
studies
revealed
the
bifunctional
ability
NIS:
mediating
formation
reactive
halogenated
intermediates
activating
them
via
halogen
bonding.
This
electrophilic
reaction
center
enables
utilization
general
heteroatom
nucleophiles,
which
are
used
limited
capacity
traditional
1,2-metalate
rearrangements.
