Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(47), С. 21674 - 21682
Опубликована: Ноя. 17, 2022
Asymmetric
sp3
C–H
functionalization
has
been
demonstrated
to
substantially
expedite
target
molecule
synthesis,
spanning
from
feedstocks
upgradation
late-stage
modification
of
complex
molecules.
Herein,
we
report
a
highly
efficient
and
sustainable
method
for
enantioselective
benzylic
cyanation
by
merging
electrophoto-
copper
catalysis.
A
novel
catalytic
system
allows
one
independently
regulate
the
hydrogen
atom
transfer
step
radical
formation
speciation
Cu(II)/Cu(I)
effectively
capture
transient
intermediate,
through
tuning
electronic
property
anthraquinone-type
photocatalyst
simply
modulating
applied
current,
respectively.
Such
decoupled
relay
catalysis
enables
unified
approach
diverse
alkylarenes,
many
which
are
much
less
reactive
or
even
unreactive
using
existing
relying
on
coupled
relay.
Moreover,
current
protocol
is
also
amenable
bioactive
molecules,
including
natural
products
drugs.
ACS Central Science,
Год журнала:
2020,
Номер
6(8), С. 1317 - 1340
Опубликована: Июль 16, 2020
As
the
breadth
of
radical
chemistry
grows,
new
means
to
promote
and
regulate
single-electron
redox
activities
play
increasingly
important
roles
in
driving
modern
synthetic
innovation.
In
this
regard,
photochemistry
electrochemistry-both
considered
as
niche
fields
for
decades-have
seen
an
explosive
renewal
interest
recent
years
gradually
have
become
a
cornerstone
organic
chemistry.
Outlook
article,
we
examine
current
state-of-the-art
areas
electrochemistry
photochemistry,
well
nascent
area
electrophotochemistry.
These
techniques
employ
external
stimuli
activate
molecules
imbue
privileged
control
reaction
progress
selectivity
that
is
challenging
traditional
chemical
methods.
Thus,
they
provide
alternative
entries
known
reactive
intermediates
enable
distinct
strategies
were
previously
unimaginable.
Of
many
hallmarks,
electro-
are
often
classified
"green"
technologies,
promoting
reactions
under
mild
conditions
without
necessity
potent
wasteful
oxidants
reductants.
This
reviews
most
growth
these
with
special
emphasis
on
conceptual
advances
given
rise
enhanced
accessibility
tools
trade.
Chemical Reviews,
Год журнала:
2021,
Номер
122(3), С. 3180 - 3218
Опубликована: Ноя. 19, 2021
Synthetic
organic
electrosynthesis
has
grown
in
the
past
few
decades
by
achieving
many
valuable
transformations
for
synthetic
chemists.
Although
electrocatalysis
been
popular
improving
selectivity
and
efficiency
a
wide
variety
of
energy-related
applications,
last
two
decades,
there
much
interest
to
develop
conceptually
novel
transformations,
selective
functionalization,
sustainable
reactions.
This
review
discusses
recent
advances
combination
electrochemistry
homogeneous
transition-metal
catalysis
synthesis.
The
enabling
mechanistic
studies
are
presented
alongside
advantages
as
well
future
directions
address
challenges
metal-catalyzed
electrosynthesis.
Green Chemistry,
Год журнала:
2020,
Номер
22(11), С. 3358 - 3375
Опубликована: Янв. 1, 2020
This
tutorial
bridges
an
important
knowledge
gap
by
providing
easily
accessible
introduction
that
enables
synthetic
chemists
to
explore
electrochemistry.
Nanoscale Horizons,
Год журнала:
2021,
Номер
6(5), С. 364 - 378
Опубликована: Янв. 1, 2021
The
nanoarchitectonics
concept
has
the
ability
to
bridge
nanoscale
science
and
visual
size
materials.
final
goal
of
approaches
is
creation
living-creature-like
functional
material
systems
from
simple
objects.
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
142(41), С. 17693 - 17702
Опубликована: Сен. 17, 2020
The
selective
installation
of
azide
groups
into
C(sp3)-H
bonds
is
a
priority
research
topic
in
organic
synthesis,
particularly
pharmaceutical
discovery
and
late-stage
diversification.
Herein,
we
demonstrate
generalized
manganese-catalyzed
oxidative
azidation
methodology
using
nucleophilic
NaN3
as
an
source
under
electrophotocatalytic
conditions.
This
approach
allows
us
to
perform
the
reaction
without
necessity
adding
excess
substrate
successfully
avoiding
use
stoichiometric
chemical
oxidants
such
iodine(III)
reagent
or
NFSI.
A
series
tertiary
secondary
benzylic
C(sp3)-H,
aliphatic
drug-molecule-based
substrates
are
well
tolerated
our
protocol.
simultaneous
gram-scale
synthesis
ease
transformation
amine
collectively
advocate
for
potential
application
preparative
synthesis.
Good
reactivity
bond
selectivity
incorporate
nitrogen-based
functionality
at
alkyl
group
also
provide
opportunities
manipulate
numerous
medicinal
candidates.
We
anticipate
synthetic
protocol,
consisting
metal
catalysis,
electrochemistry,
photochemistry,
would
new
sustainable
option
execute
challenging
transformations.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(34), С. 14275 - 14280
Опубликована: Июнь 3, 2020
Heteroarenes
are
structural
motifs
found
in
many
bioactive
compounds
and
functional
materials.
Dehydrogenative
cross-coupling
of
heteroarenes
with
aliphatic
C-H
bonds
provides
straightforward
access
to
functionalized
from
readily
available
Established
methods
employ
stoichiometric
chemical
oxidants
under
conditions
heating
or
light
irradiation.
By
merging
electrochemistry
photochemistry,
we
have
achieved
efficient
photoelectrochemical
dehydrogenative
C(sp3
)-H
donors
through
H2
evolution,
without
the
addition
metal
catalysts
oxidants.
Mechanistically,
donor
is
converted
a
nucleophilic
carbon
radical
H-atom
transfer
chlorine
atom,
which
produced
by
irradiation
anodically
generated
Cl2
Cl-
.
The
then
undergoes
substitution
heteroarene
afford
alkylated
products.
