ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(14), P. 7543 - 7551
Published: June 11, 2020
Herein,
we
report
that
merging
palladium
catalysis
with
hydrogen
atom
transfer
(HAT)
photocatalysis
enabled
direct
arylations
and
alkenylations
of
aldehyde
C–H
bonds,
facilitating
visible
light-catalyzed
construction
a
variety
ketones.
Tetrabutylammonium
decatungstate
anthraquinone
were
found
to
act
as
synergistic
HAT
photocatalysts.
Density
functional
theory
calculations
suggested
Pd0–PdII–PdIII–PdI–Pd0
pathway
revealed
regeneration
the
Pd0
catalyst
photocatalyst
occurs
simultaneously
in
presence
KHCO3.
This
features
low
energy
barrier,
promoting
efficient
coupling
catalytic
cycle
photocatalytic
cycle.
The
work
reported
herein
suggests
great
promise
for
further
applications
palladium-catalyzed
cross-coupling
C-H
functionalization
reactions
be
successful.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1485 - 1542
Published: Nov. 18, 2021
The
merger
of
photoredox
catalysis
with
transition
metal
catalysis,
termed
metallaphotoredox
has
become
a
mainstay
in
synthetic
methodology
over
the
past
decade.
Metallaphotoredox
combined
unparalleled
capacity
for
bond
formation
broad
utility
photoinduced
electron-
and
energy-transfer
processes.
Photocatalytic
substrate
activation
allowed
engagement
simple
starting
materials
metal-mediated
bond-forming
Moreover,
electron
or
energy
transfer
directly
key
organometallic
intermediates
provided
novel
modes
entirely
complementary
to
traditional
catalytic
platforms.
This
Review
details
contextualizes
advancements
molecule
construction
brought
forth
by
metallaphotocatalysis.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
59(1), P. 74 - 108
Published: May 22, 2019
Abstract
Radical–radical
couplings
are
mostly
nearly
diffusion‐controlled
processes.
Therefore,
the
selective
cross‐coupling
of
two
different
radicals
is
challenging
and
not
a
synthetically
valuable
transformation.
However,
if
have
lifetimes
they
generated
at
equal
rates,
will
become
dominant
process.
This
high
cross‐selectivity
based
on
kinetic
phenomenon
called
persistent
radical
effect
(PRE).
In
this
Review,
an
explanation
PRE
supported
by
simulations
simple
model
systems
provided.
Radical
stabilities
discussed
within
context
their
lifetimes,
various
examples
PRE‐mediated
radical–radical
in
synthesis
summarized.
It
shown
that
restricted
to
coupling
with
transient
radical.
If
one
partner
longer‐lived
than
other
radical,
operates
achieved.
important
point
expands
scope
chemistry.
The
Review
divided
into
parts,
namely
1)
or
organic
2)
“radical–metal
crossover
reactions”;
here,
metal‐centered
species
more
generally
transition‐metal
complexes
able
react
discussed—a
field
has
flourished
recently.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1925 - 2016
Published: Sept. 29, 2021
The
fields
of
C–H
functionalization
and
photoredox
catalysis
have
garnered
enormous
interest
utility
in
the
past
several
decades.
Many
different
scientific
disciplines
relied
on
strategies
including
natural
product
synthesis,
drug
discovery,
radiolabeling,
bioconjugation,
materials,
fine
chemical
synthesis.
In
this
Review,
we
highlight
use
reactions.
We
separate
review
into
inorganic/organometallic
catalysts
organic-based
catalytic
systems.
Further
subdivision
by
reaction
class─either
sp2
or
sp3
functionalization─lends
perspective
tactical
for
these
methods
synthetic
applications.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2017 - 2291
Published: Nov. 23, 2021
We
present
here
a
review
of
the
photochemical
and
electrochemical
applications
multi-site
proton-coupled
electron
transfer
(MS-PCET)
in
organic
synthesis.
MS-PCETs
are
redox
mechanisms
which
both
an
proton
exchanged
together,
often
concerted
elementary
step.
As
such,
MS-PCET
can
function
as
non-classical
mechanism
for
homolytic
bond
activation,
providing
opportunities
to
generate
synthetically
useful
free
radical
intermediates
directly
from
wide
variety
common
functional
groups.
introduction
practitioner’s
guide
reaction
design,
with
emphasis
on
unique
energetic
selectivity
features
that
characteristic
this
class.
then
chapters
oxidative
N–H,
O–H,
S–H,
C–H
homolysis
methods,
generation
corresponding
neutral
species.
Then,
reductive
PCET
activations
involving
carbonyl,
imine,
other
X═Y
π-systems,
heteroarenes,
where
ketyl,
α-amino,
heteroarene-derived
radicals
be
generated.
Finally,
we
asymmetric
catalysis
materials
device
applications.
Within
each
chapter,
subdivide
by
group
undergoing
homolysis,
thereafter
type
transformation
being
promoted.
Methods
published
prior
end
December
2020
presented.
Chemical Society Reviews,
Journal Year:
2020,
Volume and Issue:
50(2), P. 766 - 897
Published: Dec. 22, 2020
Recent
developments
and
future
prospects
of
visible-light
photocatalysis
in
the
late-stage
functionalization
pharmaceuticals
natural
bioactive
compounds.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(25), P. 8572 - 8576
Published: April 1, 2019
Abstract
A
systematic,
user‐friendly
assessment
tool
that
delivers
a
clear
overview
of
the
sensitivity
reactions
to
key
parameters
is
highly
desirable.
Herein,
development
such
method
described.
The
intuitive,
standardized
presentation
results
in
radar
diagram
enables
protocol
be
rapidly
assessed.
This
was
applied
five
different
visible‐light‐mediated
photochemical
reactions,
and
were
correlated
underlying
mechanism.
Ultimately,
we
believe
this
will
help
increase
uptake
new
synthetic
methods
their
reproducibility.
Chemical Science,
Journal Year:
2019,
Volume and Issue:
10(36), P. 8285 - 8291
Published: Jan. 1, 2019
The
concept
of
reductive
radical-polar
crossover
(RRPCO)
reactions
has
recently
emerged
as
a
valuable
and
powerful
tool
to
overcome
limitations
both
radical
traditional
polar
chemistry.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
60(4), P. 1714 - 1726
Published: July 17, 2020
Metallaphotoredox
catalysis
has
evolved
into
an
enabling
platform
to
construct
C(sp3
)-hybridized
centers
under
remarkably
mild
reaction
conditions.
The
cultivation
of
abundant
radical
precursor
feedstocks
significantly
increased
the
scope
transition-metal-catalyzed
cross-couplings,
especially
with
respect
C(sp2
)-C(sp3
)
linkages.
In
recent
years,
considerable
effort
been
devoted
understanding
origin
stereoinduction
in
dual
catalytic
processes.
this
context,
Ni-
and
Cu-catalyzed
transformations
have
played
a
predominant
role
exploiting
mode
catalysis.
Herein,
we
provide
critical
overview
on
progress
enantioselective
bond
formations
enabled
by
manifolds.
Furthermore,
selected
stereochemical
control
elements
within
realm
diastereoselective
are
discussed.
