Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 4, 2025
Traditional
reductions
of
alkenes,
such
as
using
stoichiometric
reductants
with
waste
generation
and
catalytic
hydrogenation
high-pressure
H2,
are
accompanied
by
environmental
or
safety
issues.
Herein,
we
demonstrated
a
universal
method
for
the
electrocatalytic
deuteration
alkenes
modified
electrodes
under
ambient
temperature.
The
key
M-H/M-D
species
alkene
reduction
were
generated
from
electrolysis
H2O/D2O
on
electrodes,
which
avoided
usage
H2
D2.
Mono-,
di-,
tri-,
tetra-substituted
successfully
reduced
in
this
system
H2O
D2O
hydrogen
deuterium
sources.
Electron-donating/-withdrawing
other
easily
reducible
functional
groups,
complicated
natural
products
drugs
all
reductive
hydrogenated
deuterated
excellent
yields
(85
examples,
up
to
99%).
Faraday
efficiency
efficient
could
reach
84%.
Moreover,
amount
metal
decrease
less
than
0.01
mol
%.
eScience,
Год журнала:
2022,
Номер
2(3), С. 243 - 277
Опубликована: Апрель 23, 2022
Compared
with
general
redox
chemistry,
electrochemistry
using
the
electron
as
a
potent,
controllable,
yet
traceless
alternative
to
chemical
oxidants/reductants
usually
offers
more
sustainable
options
for
achieving
selective
organic
synthesis.
With
its
environmentally
benign
features
gradually
being
uncovered
and
studied,
electrosynthesis
is
currently
undergoing
revival
becoming
rapidly
growing
area
within
synthetic
community.
Among
electrochemical
transformations,
anodically
enabled
ones
have
been
far
extensively
exploited
than
those
driven
by
cathodic
reduction,
although
both
approaches
are
conceptually
attractive.
To
stimulate
development
of
cathodically
reactions,
this
review
summarizes
recently
developed
reductive
electrosynthetic
protocols,
discussing
highlighting
reaction
features,
substrate
scopes,
applications,
plausible
mechanisms
reveal
recent
trends
in
area.
Herein,
reduction-enabled
preparative
transformations
categorized
into
four
types:
reduction
(1)
unsaturated
hydrocarbons,
(2)
heteroatom-containing
carbon-based
systems,
(3)
saturated
C-hetero
or
C–C
polar/strained
bonds,
(4)
hetero-hetero
linkages.
Apart
from
net
electroreductive
few
examples
photo-electrosynthesis
well
paired
electrolysis
also
introduced,
which
offer
opportunities
overcome
certain
limitations
improve
versatility.
The
electrochemically
driven,
transition
metal-catalyzed
cross-couplings
that
comprehensively
discussed
several
other
reviews
not
included
here.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(9), С. 5349 - 5365
Опубликована: Янв. 1, 2021
Ketyl
radicals
are
valuable
reactive
intermediates
for
synthesis
and
used
extensively
to
construct
complex,
functionalized
products
from
carbonyl
substrates.
Single
electron
transfer
(SET)
reduction
of
the
C[double
bond,
length
as
m-dash]O
bond
aldehydes
ketones
is
classical
approach
formation
ketyl
metal
reductants
archetypal
reagents
employed.
The
past
decade
has,
however,
witnessed
significant
advances
in
generation
harnessing
radicals.
This
tutorial
review
highlights
recent,
exciting
developments
chemistry
by
comparing
varied
contemporary
-
example,
using
photoredox
catalysts
more
approaches
use
will
focus
on
different
strategies
radical
generation,
their
creative
new
synthetic
protocols,
control
enantioselectivity,
detailed
mechanisms
where
appropriate.
Advanced Synthesis & Catalysis,
Год журнала:
2021,
Номер
364(2), С. 234 - 267
Опубликована: Ноя. 29, 2021
Abstract
Fluorine‐containing
moieties
are
widely
used
in
the
pharmaceutical,
agrochemical,
and
material
fields.
Thus,
these
structures
of
immense
interest
fields
organic
synthesis
medicinal
chemistry.
Among
various
fluorinated
groups,
difluoromethyl
unit
has
drawn
increasing
attention
due
to
its
unique
pharmaceutical
properties.
In
recent
years,
several
methods
for
difluoromethylated
compounds
have
been
rapidly
developed.
However,
most
treat
aromatic
with
excess
difluoromethylating
reagents,
which
often
contain
organometallic
compounds,
so
transformations
generally
less
environmentally
friendly
atom‐economical.
this
review,
we
summarize
development
new
motifs
or
difluoroalkenes
from
trifluoromethylated
trifluoromethyl
alkenes
via
single
C(
sp
3
)−F
bond
cleavage.
magnified
image
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(30), С. 11602 - 11610
Опубликована: Июль 22, 2021
Herein
we
report
a
chromium-catalyzed
allylic
defluorinative
ketyl
olefin
coupling
between
aldehydes
and
α-trifluoromethyl
alkenes,
which
provides
novel
efficient
access
to
diverse
gem-difluorohomoallylic
alcohols.
Remarkably,
the
high
chemoselectivity
of
this
reaction
enables
conversion
formyl
moiety
in
presence
various
easily
reducible
functionalities
including
ketone,
organohalides,
aziridine,
sulfone,
alkyne,
unactivated
alkene.
The
utility
method
is
demonstrated
by
simple
derivatizations
attached
hydroxyl
group
products.
preliminary
mechanistic
investigations
suggest
pathway
with
rate-limiting
C–C
forming
step
followed
facile
β-fluoro
elimination.
ACS Central Science,
Год журнала:
2021,
Номер
7(8), С. 1347 - 1355
Опубликована: Авг. 5, 2021
Organic
electrochemistry
has
emerged
as
an
enabling
and
sustainable
technology
in
modern
organic
synthesis.
Despite
the
recent
renaissance
of
electrosynthesis,
broad
adoption
synthetic
community,
especially
industrial
settings,
been
hindered
by
lack
general,
standardized
platforms
for
high-throughput
experimentation
(HTE).
Herein,
we
disclose
design
HT
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(23)
Опубликована: Апрель 3, 2023
Carboxylation
of
easily
available
alkenes
with
CO2
is
highly
important
to
afford
value-added
carboxylic
acids.
Although
dicarboxylation
activated
alkenes,
especially
1,3-dienes,
has
been
widely
investigated,
the
challenging
unactivated
1,n-dienes
(n>3)
remains
unexplored.
Herein,
we
report
first
skipped
dienes
via
electrochemistry,
affording
valuable
dicarboxylic
Control
experiments
and
DFT
calculations
support
single
electron
transfer
(SET)
reduction
its
radical
anion,
which
followed
by
sluggish
addition
SET
unstabilized
alkyl
radicals
carbanions
nucleophilic
attack
on
give
desired
products.
This
reaction
features
mild
conditions,
broad
substrate
scope,
facile
derivations
products
promising
application
in
polymer
chemistry.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(20), С. 10967 - 10973
Опубликована: Апрель 19, 2023
Despite
the
widespread
applications
of
α-hydroxyalkyl
cyclic
amines,
direct
and
diverse
access
to
such
a
class
unique
vicinal
amino
alcohols
still
remains,
date,
challenge.
Here,
through
strategy
electroreductive
α-hydroxyalkylation
inactive
N-heteroarenes
with
ketones
or
electron-rich
arylaldehydes,
we
describe
room
temperature
approach
for
construction
which
features
broad
substrate
scope,
operational
simplicity,
high
chemoselectivity,
no
need
pressurized
H2
gas
transition
metal
catalysts.
The
zinc
ion
generated
from
anode
oxidation
plays
crucial
role
in
activation
both
reactants
by
decreasing
their
reduction
potentials.
electroreduction
combination
Lewis
acids
this
work
is
anticipated
develop
more
useful
transformations.
