Organic Letters,
Год журнала:
2023,
Номер
26(1), С. 411 - 415
Опубликована: Дек. 26, 2023
We
report
a
strategic
exploitation
of
trifluoromethyl
thianthrenium
triflate
(TT-CF3+OTf–)
as
both
electromediator
and
CF3
radical
precursors
for
paired
electrolysis.
Enabled
by
this
strategy,
the
three-component
trifluoromethylheteroaromatization
alkenes
alkynes
was
realized.
The
superiority
TT-CF3+OTf–
to
other
electrophilic
reagents
is
attributed
cathodic
generation
thianthrene
(TT)
mediator,
which
shifts
heterogeneous
oxidation
interest
homogeneous
one.
The Journal of Physical Chemistry C,
Год журнала:
2025,
Номер
129(6), С. 3014 - 3021
Опубликована: Фев. 3, 2025
The
formation
of
substituted
benzyl
alcohols
from
dicyanobenzenes
and
methanol
(C–C
coupling)
is
demonstrated
as
a
model
system
for
paired
electrosynthesis
investigated
at
interdigitated
microband
array
electrodes
in
microreactor
with/without
intentionally
added
supporting
electrolyte.
A
Pt–Pt
with
5
μm
bands
separated
by
gaps
employed
dimethyl
sulfoxide
(DMSO)
solvent.
Yields
are
optimized
to
approximately
50%
the
point
100%
conversion.
mechanism
employing
isotope
labeling
(CD3OD,
CH3OD,
d6-DMSO,
13CH3OH).
methylene
group
(12C
or
13C)
obtained
H2,
D2,
DH
substitution
patterns,
hypothesis
corresponding
discussed
aided
density
functional
theory
(DFT)
calculations.
Implications
sustainable
discussed.
ACS Macro Letters,
Год журнала:
2024,
Номер
unknown, С. 1345 - 1354
Опубликована: Сен. 25, 2024
Electrolysis
is
an
emerging
approach
to
polymer
postpolymerization
modification,
deconstruction,
and
depolymerization.
Electrochemical
reactions
are
particularly
appealing
for
macromolecular
transformations
because
of
their
high
selectivity,
ability
be
externally
monitored,
intrinsic
scalability.
Despite
these
desirable
features
the
recent
resurgent
use
small-molecule
electrochemical
reactions,
development
electrolysis
has
been
limited.
Herein,
we
highlight
examples
driven
by
heterogeneous
redox
chemistry.
Throughout
our
exploration
electrolysis,
provide
perspective
on
opportunities
continued
investigation
in
this
nascent
field.
Specifically,
how
targeted
reaction
through
deeper
mechanistic
insight
will
expand
scope
materials
that
can
(de)constructed
with
methods.
As
developed,
expect
emerge
as
a
high-functioning
complementary
tool
functionalization
deconstruction.
Chemical Communications,
Год журнала:
2024,
Номер
60(48), С. 6174 - 6177
Опубликована: Янв. 1, 2024
The
electro-generation
of
acyl
radicals
from
both
aromatic
and
aliphatic
aldehydes
is
a
synthetic
challenge.
We
addressed
this
challenge
by
merging
electro-oxidation
quinuclidine-mediated
HAT
strategy.
Chemical Science,
Год журнала:
2024,
Номер
15(33), С. 13459 - 13465
Опубликована: Янв. 1, 2024
An
unprecedented
radical
smiles
rearrangement
of
N
-arylpropiolamides
was
realized
by
merging
electro-reduction
with
hydrogen
bonding
activation.
Enabled
this
dual
activation
strategy,
the
reduction
potential
shifted
positively
218
mV.
