An
electroreductive
annulation
reaction
of
1,10-phenanthrolines
and
imines
has
been
developed.
This
method
proceeds
with
broad
substrate
functionality
tolerance,
high
selectivity,
no
need
for
pressurized
H2
gas
or
transition
metal
catalysts.
Mechanistic
studies
reveal
that
the
products
are
formed
via
simultaneous
electroreduction
both
proton-activated
reactants
followed
by
radical
cross-coupling
intramolecular
cyclization
coupling
adduct.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(45)
Опубликована: Сен. 12, 2023
Despite
widespread
use
of
the
deuterium
isotope
effect,
selective
labeling
chemical
molecules
remains
a
major
challenge.
Herein,
facile
and
general
electrochemically
driven,
organic
mediator
enabled
deuteration
styrenes
with
oxide
(D2
O)
as
economical
source
was
reported.
Importantly,
this
transformation
could
be
suitable
for
various
electron
rich
mediated
by
triphenylphosphine
(TPP).
The
reaction
proceeded
under
mild
conditions
without
transition-metal
catalysts,
affording
desired
products
in
good
yields
excellent
D-incorporation
(D-inc,
up
to
>99
%).
Mechanistic
investigations
means
experiments
cyclic
voltammetry
tests
provided
sufficient
support
transformation.
Notably,
method
proved
powerful
tool
late-stage
biorelevant
compounds.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 30, 2024
Abstract
Herein,
we
report
an
electroreduction
of
unactivated
alkyl
alkenes
enabled
by
[Fe]-H,
which
is
provided
through
the
combination
anodic
iron
salts
and
silane
generated
in
situ
via
cathodic
reduction,
using
H
2
O
as
H-source.
The
catalytic
amounts
Si-additive
work
H-carrier
from
to
generate
a
highly
active
species
under
continuous
electrochemical
conditions.
This
approach
shows
broad
substrate
scope
good
functional
group
compatibility.
In
addition
hydrogenation,
use
D
instead
provides
desired
deuterated
products
yields
with
excellent
D-incorporation
(up
>99%).
Further
late-stage
hydrogenation
complex
molecules
drug
derivatives
demonstrate
potential
application
pharmaceutical
industry.
Mechanistic
studies
are
performed
provide
support
for
proposed
mechanistic
pathway.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(37), С. 20169 - 20175
Опубликована: Сен. 7, 2023
Herein,
we
report
a
new
class
of
electrophotocatalysts,
polycyclic
aromatic
hydrocarbons,
that
promote
the
reduction
unactivated
carbonyl
compounds
to
generate
versatile
ketyl
radical
intermediates.
This
catalytic
platform
enables
previously
challenging
intermolecular
coupling
reactions,
including
those
classic
reductants
(e.g.,
SmI2/HMPA)
have
failed
promote.
More
broadly,
this
study
outlines
an
approach
fundamentally
expand
array
reactive
intermediates
can
be
generated
via
electrophotocatalysis
by
obviating
need
for
rapid
mesolytic
cleavage
following
substrate
reduction.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(44)
Опубликована: Сен. 14, 2023
Herein,
an
electrochemically
driven
NiH-catalyzed
reductive
coupling
of
alkyl
halides
and
alkenes
for
the
construction
Csp3
-Csp3
bonds
is
firstly
reported.
Notably,
serve
dual
function
as
substrates
hydrogen
sources
to
generate
NiH
species
under
electrochemical
conditions.
The
tunable
nature
this
reaction
realized
by
introducing
intramolecular
coordinating
group
substrate,
where
product
can
be
easily
adjusted
give
desired
branched
products.
method
proceeds
mild
conditions,
exhibits
a
broad
substrate
scope,
affords
moderate
excellent
yields
with
over
70
examples,
including
late-stage
modification
natural
products
drug
derivatives.
Mechanistic
insights
offer
evidence
process.
sp3
-carbon-halogen
activated
through
single
electron
transfer
(SET)
nickel
catalyst
in
its
low
valence
state,
generated
cathodic
reduction,
generation
from
pivotal
transformation.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(5), С. 795 - 813
Опубликована: Фев. 23, 2024
ConspectusThe
selective
functionalization/transformation
of
ubiquitous
pyridine-fused
N-heteroarenes
is
a
practical
method
to
synthesize
structurally
novel
N-heterocycles,
which
important
for
the
development
medicines,
bioactive
agents,
agrochemicals,
materials,
ligands,
sensors,
pigments,
dyes,
etc.
However,
owing
thermodynamic
stability,
kinetic
inertness,
and
lone
electron
pair–induced
catalyst
deactivation
N-heteroarenes,
limited
strategies
(e.g.,
C–H
activation/functionalization,
electrophilic
substitution,
Minisci
reaction)
are
available
realize
synthetic
purpose
maintain
aromaticity
final
products.
Moreover,
relevant
transformations
have
limitations
such
as
needing
harsh
reaction
conditions,
requiring
preinstallation
specific
coupling
agents
containing
transformable
functionalities
or
directing
groups,
using
less
environmentally
benign
oxidants
and/or
acidic
activators,
poor
selectivity.
Herein,
considering
that
imines,
enamines,
radicals,
cyclic
amines
generated
during
reduction
precise
transformation
these
reductive
intermediates
offers
fundamental
basis
developing
tandem
reactions.
Our
group
revealed
slow
rate,
synergistic
catalysis,
controlled
electroreduction
effective
fulfilling
functionalization
N-heteroarenes.
Thus,
we
established
series
new
methods
provide
diverse
construction
modalities
functionalized
N-heterocycles.
The
striking
features
include
high
efficiency,
atom
economy,
use
readily
accessible
feedstocks
in
absence
flammable
pressurized
H2
gas,
alongside
promising
potential
obtained
N-heterocyclic
present
study
would
be
appealing
fields
organic
chemistry,
biomedical
functional
materials.
This
Account
describes
application
dearomatization
substrate-activating
reaction-initiating
modes
summarizes
via
alkylation,
arylation,
annulation
at
nitrogen,
α,
β,
other
remote
carbon
sites
achieved
over
past
8
years.
Details
regarding
reactions
their
plausible
mechanisms
perspectives
discussed.
We
hope
our
contributions
this
field
will
aid
further
tackle
intractable
challenges
area.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Май 7, 2024
Herein,
we
develop
a
straightforward,
metal-free,
and
acid-/base-free
electrochemical
C4-selective
C
-
H
deuteration
of
pyridine
derivatives
with
economic
convenient
D
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Окт. 13, 2023
Herein,
a
metal-free
electrochemical
dihydroxylation
of
unactivated
alkenes
is
described.
The
transformation
proceeds
smoothly
under
mild
conditions
with
broad
range
alkenes,
providing
valuable
and
versatile
dihydroxylated
products
in
moderate
to
good
yields
without
the
addition
costly
transition
metals
stoichiometric
amounts
chemical
oxidants.
Moreover,
this
method
can
be
applied
natural
pharmaceutical
derivatives,
further
demonstrating
its
synthetic
utility.
Mechanistic
studies
have
revealed
that
iodohydrin
epoxide
intermediate
are
formed
during
reaction
process.
We
have
developed
a
mild
and
efficient
electrochemical
reduction
approach
employing
aryl
diazonium
salts
as
dual
synthons
to
synthesize
valuable
multi-substituted
pyrazoles
for
the
first
time.
Organic Letters,
Год журнала:
2024,
Номер
26(3), С. 607 - 612
Опубликована: Янв. 11, 2024
An
electrochemical
approach
to
biheteroaryls
through
the
coupling
of
diverse
N-heteroarenes
with
heteroaryl
phosphonium
salts
is
reported.
The
reaction
features
pH
and
redox-neutral
conditions
excellent
regioselectivity,
as
well
exogenous
air
or
moisture
tolerance.
Additionally,
a
one-pot,
two-step
protocol
can
be
established
realize
formal
C–H/C–H
heteroarenes,
thereby
greatly
expanding
substrate
availability.
utility
this
method
demonstrated
late-stage
functionalization,
total
synthesis
nitraridine,
antifungal
activity
studies.
