Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(39), P. 21100 - 21115
Published: Feb. 18, 2021
Abstract
The
mainstream
applications
of
visible‐light
photoredox
catalysis
predominately
involve
outer‐sphere
single‐electron
transfer
(SET)
or
energy
(EnT)
processes
precious
metal
Ru
II
Ir
III
complexes
organic
dyes
with
low
photostability.
Earth‐abundant
metal‐based
M
n
L
‐type
(M=metal,
=polydentate
ligands)
are
rapidly
evolving
as
alternative
photocatalysts
they
offer
not
only
economic
and
ecological
advantages
but
also
access
to
the
complementary
inner‐sphere
mechanistic
modes,
thereby
transcending
their
inherent
limitations
ultrashort
excited‐state
lifetimes
for
use
effective
photocatalysts.
generic
process,
termed
visible‐light‐induced
homolysis
(VLIH),
entails
formation
suitable
light‐absorbing
ligated
metal–substrate
(M
‐Z;
Z=substrate)
that
can
undergo
homolytic
cleavage
generate
n−1
Z
.
further
transformations.
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(16), P. 9170 - 9196
Published: July 20, 2020
The
development
of
transition
metal
(TM)
catalysis
for
organic
synthesis
under
visible
light
without
recourse
to
typical
photoredox
catalysts
has
become
a
rapidly
growing
area
research
and
been
actively
explored
in
the
past
several
years.
Distinct
from
extensively
developed
catalysis,
which
photocatalyst
generally
does
not
directly
participate
bond-forming
process,
photocatalyst/TM
synergistic
absorbs
photon
energy
transfers
TM
catalyst
through
redox
or
transfer
this
Review
focuses
on
summarizing
recent
developments
photocatalytic
reactions
that
use
complexes
both
absorb
catalytic
bond
formation
involving
covalently
bonded
intermediate.
contents
are
categorized
by
used
(Pd,
Cu,
Co,
Ni,
Mn,
Au,
Rh,
Fe,
Ru),
with
descending
sequence
according
number
examples
reported
each
metal,
provide
an
overview
April
2020.
Future
perspectives
personal
opinions
regarding
expanding
field
also
discussed.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2650 - 2694
Published: Aug. 27, 2021
Geometrical
E
→
Z
alkene
isomerization
is
intimately
entwined
in
the
historical
fabric
of
organic
photochemistry
and
enjoying
a
renaissance
(Roth
et
al.
Angew.
Chem.,
Int.
Ed.
Engl.
1989
28,
1193–1207).
This
consequence
fundamental
stereochemical
importance
Z-alkenes,
juxtaposed
with
frustrations
thermal
reactivity
that
are
rooted
microscopic
reversibility.
Accessing
excited
state
paradigms
allow
this
latter
obstacle
to
be
circumnavigated
by
exploiting
subtle
differences
photophysical
behavior
substrate
product
chromophores:
provides
molecular
basis
for
directionality.
While
direct
irradiation
operationally
simple,
photosensitization
via
selective
energy
transfer
enables
augmentation
repertoire
include
substrates
not
directly
photons.
Through
sustained
innovation,
an
impressive
portfolio
tailored
small
molecule
catalysts
range
triplet
energies
now
widely
available
facilitate
contra-thermodynamic
thermo-neutral
reactions
generate
Z-alkene
fragments.
review
intended
serve
as
practical
guide
covering
geometric
alkenes
enabled
catalysis
from
2000
2020,
logical
sequel
excellent
treatment
Dugave
Demange
(Chem.
Rev.
2003
103,
2475–2532).
The
mechanistic
foundations
underpinning
selectivity
discussed
together
induction
models
rationales
explain
counterintuitive
directionality
these
processes
which
very
distinguish
product.
Implications
subsequent
stereospecific
transformations,
application
total
synthesis,
regioselective
polyene
isomerization,
spatiotemporal
control
pre-existing
configuration
broader
sense
discussed.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(38), P. 12200 - 12209
Published: Sept. 5, 2018
Triplet
ketone
sensitizers
are
of
central
importance
within
the
realm
photochemical
transformations.
Although
radical-type
character
triplet
excited
states
diaryl
ketones
suggests
viability
for
triggering
hydrogen-atom
transfer
(HAT)
and
single-electron
(SET)
processes,
among
others,
their
use
as
multifaceted
catalysts
in
C–C
bond-formation
via
sp3
C–H
functionalization
alkane
feedstocks
still
remains
rather
unexplored.
Herein,
we
unlock
a
modular
platform
forging
C(sp3)–C(sp2)
C(sp3)–C(sp3)
linkages
from
abundant
bonds
functional
handles
using
synergy
between
nickel
simple,
cheap
ketones.
This
method
is
distinguished
by
its
wide
scope
that
obtained
starting
precursors,
thus
complementing
existing
inner-sphere
protocols
or
recent
photoredox
scenarios
based
on
iridium
polypyridyl
complexes.
Additionally,
such
provides
new
strategy
streamlining
synthesis
complex
molecules
with
high
levels
predictable
site-selectivity
preparative
utility.
Mechanistic
experiments
suggest
abstraction
occurs
HAT
state.
We
believe
this
study
will
contribute
to
more
systematic
utilization
metallaphotoredox
scenarios.
ACS Catalysis,
Journal Year:
2019,
Volume and Issue:
9(5), P. 4115 - 4144
Published: April 9, 2019
Light
has
received
increased
attention
for
various
chemical
reactions
but
also
in
combination
with
biocatalytic
reactions.
Because
currently
only
a
few
enzymatic
are
known,
which
per
se
require
light,
most
transformations
involving
light
and
biocatalyst
exploit
either
providing
the
cosubstrate
or
cofactor
an
appropriate
redox
state
biotransformation.
In
selected
cases,
promiscuous
activity
of
known
enzymes
presence
could
be
induced.
other
approaches,
light-induced
have
been
combined
step,
were
linear
cascade.
Finally,
switchable
moiety
investigated
to
turn
off/on
tune
actual
reaction.
This
Review
gives
overview
approaches
using
biocatalysis.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(39), P. 21100 - 21115
Published: Feb. 18, 2021
Abstract
The
mainstream
applications
of
visible‐light
photoredox
catalysis
predominately
involve
outer‐sphere
single‐electron
transfer
(SET)
or
energy
(EnT)
processes
precious
metal
Ru
II
Ir
III
complexes
organic
dyes
with
low
photostability.
Earth‐abundant
metal‐based
M
n
L
‐type
(M=metal,
=polydentate
ligands)
are
rapidly
evolving
as
alternative
photocatalysts
they
offer
not
only
economic
and
ecological
advantages
but
also
access
to
the
complementary
inner‐sphere
mechanistic
modes,
thereby
transcending
their
inherent
limitations
ultrashort
excited‐state
lifetimes
for
use
effective
photocatalysts.
generic
process,
termed
visible‐light‐induced
homolysis
(VLIH),
entails
formation
suitable
light‐absorbing
ligated
metal–substrate
(M
‐Z;
Z=substrate)
that
can
undergo
homolytic
cleavage
generate
n−1
Z
.
further
transformations.