Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(34), P. 18753 - 18759
Published: Aug. 15, 2023
The
asymmetric
difunctionalization
of
alkenes,
a
method
transforming
readily
accessible
alkenes
into
enantioenriched
chiral
structures
high
value,
has
long
been
focal
point
organic
synthesis.
Despite
tremendous
efforts
in
this
domain,
it
remains
considerable
challenge
to
devise
enantioselective
oxidative
dicarbofunctionalization
even
though
these
transformations
can
utilize
stable
and
unfunctionalized
functional
group
donors.
In
context,
we
report
herein
photoelectrocatalytic
for
the
heteroarylcyanation
aryl
which
employs
heteroarenes
through
C-H
functionalization.
photoelectrochemical
catalysis
(PEAC)
combines
photoredox
electrocatalysis
facilitate
formation
two
C-C
bonds
operating
via
hydrogen
(H2)
evolution
obviating
need
external
chemical
oxidants.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(14), P. 7941 - 8002
Published: Jan. 1, 2021
Electrochemistry
has
recently
gained
increased
attention
as
a
versatile
strategy
for
achieving
challenging
transformations
at
the
forefront
of
synthetic
organic
chemistry.
Electrochemistry's
unique
ability
to
generate
highly
reactive
radical
and
ion
intermediates
in
controlled
fashion
under
mild
conditions
inspired
development
number
new
electrochemical
methodologies
preparation
valuable
chemical
motifs.
Particularly,
recent
developments
electrosynthesis
have
featured
an
use
redox-active
electrocatalysts
further
enhance
control
over
selective
formation
downstream
reactivity
these
intermediates.
Furthermore,
electrocatalytic
mediators
enable
proceed
manner
that
is
mechanistically
distinct
from
purely
methods,
allowing
subversion
kinetic
thermodynamic
obstacles
encountered
conventional
synthesis.
This
review
highlights
key
innovations
within
past
decade
area
electrocatalysis,
with
emphasis
on
mechanisms
catalyst
design
principles
underpinning
advancements.
A
host
oxidative
reductive
are
discussed
grouped
according
classification
transformation
nature
electrocatalyst.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1875 - 1924
Published: Aug. 6, 2021
Direct
photocatalyzed
hydrogen
atom
transfer
(d-HAT)
can
be
considered
a
method
of
choice
for
the
elaboration
aliphatic
C–H
bonds.
In
this
manifold,
photocatalyst
(PCHAT)
exploits
energy
photon
to
trigger
homolytic
cleavage
such
bonds
in
organic
compounds.
Selective
bond
may
achieved
by
judicious
abstractor
(key
parameters
are
electronic
character
and
molecular
structure),
as
well
reaction
additives.
Different
classes
PCsHAT
available,
including
aromatic
ketones,
xanthene
dyes
(Eosin
Y),
polyoxometalates,
uranyl
salts,
metal-oxo
porphyrin
tris(amino)cyclopropenium
radical
dication.
The
processes
(mainly
C–C
formation)
most
cases
carried
out
under
mild
conditions
with
help
visible
light.
aim
review
is
offer
comprehensive
survey
synthetic
applications
d-HAT.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2752 - 2906
Published: Aug. 10, 2021
Photoinduced
chemical
transformations
have
received
in
recent
years
a
tremendous
amount
of
attention,
providing
plethora
opportunities
to
synthetic
organic
chemists.
However,
performing
photochemical
transformation
can
be
quite
challenge
because
various
issues
related
the
delivery
photons.
These
challenges
barred
widespread
adoption
steps
industry.
past
decade,
several
technological
innovations
led
more
reproducible,
selective,
and
scalable
photoinduced
reactions.
Herein,
we
provide
comprehensive
overview
these
exciting
advances,
including
flow
chemistry,
high-throughput
experimentation,
reactor
design
scale-up,
combination
photo-
electro-chemistry.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2487 - 2649
Published: Nov. 9, 2021
Redox
processes
are
at
the
heart
of
synthetic
methods
that
rely
on
either
electrochemistry
or
photoredox
catalysis,
but
how
do
and
catalysis
compare?
Both
approaches
provide
access
to
high
energy
intermediates
(e.g.,
radicals)
enable
bond
formations
not
constrained
by
rules
ionic
2
electron
(e)
mechanisms.
Instead,
they
1e
mechanisms
capable
bypassing
electronic
steric
limitations
protecting
group
requirements,
thus
enabling
chemists
disconnect
molecules
in
new
different
ways.
However,
while
providing
similar
intermediates,
differ
several
physical
chemistry
principles.
Understanding
those
differences
can
be
key
designing
transformations
forging
disconnections.
This
review
aims
highlight
these
similarities
between
comparing
their
underlying
principles
describing
impact
electrochemical
photochemical
methods.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(8), P. 4237 - 4352
Published: Jan. 24, 2023
The
emergence
of
modern
photocatalysis,
characterized
by
mildness
and
selectivity,
has
significantly
spurred
innovative
late-stage
C–H
functionalization
approaches
that
make
use
low
energy
photons
as
a
controllable
source.
Compared
to
traditional
strategies,
photocatalysis
paves
the
way
toward
complementary
and/or
previously
unattainable
regio-
chemoselectivities.
Merging
compelling
benefits
with
workflow
offers
potentially
unmatched
arsenal
tackle
drug
development
campaigns
beyond.
This
Review
highlights
photocatalytic
strategies
small-molecule
drugs,
agrochemicals,
natural
products,
classified
according
targeted
bond
newly
formed
one.
Emphasis
is
devoted
identifying,
describing,
comparing
main
mechanistic
scenarios.
draws
critical
comparison
between
established
ionic
chemistry
photocatalyzed
radical-based
manifolds.
aims
establish
current
state-of-the-art
illustrate
key
unsolved
challenges
be
addressed
in
future.
authors
aim
introduce
general
readership
functionalization,
specialist
practitioners
evaluation
methodologies,
potential
for
improvement,
future
uncharted
directions.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(41), P. 17693 - 17702
Published: Sept. 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.
Green Chemistry,
Journal Year:
2021,
Volume and Issue:
23(18), P. 6789 - 6862
Published: Jan. 1, 2021
We
provide
a
review
of
the
progress
cross-dehydrogenative
coupling
reactions
in
constructing
wide
variety
C–C
bonds.
Sustainable
can
be
combined
with
multiple
forms
energy
output.