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 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.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(12), P. 10599 - 10650
Published: March 1, 2022
Proton-coupled
electron
transfer
(PCET)
plays
an
essential
role
in
a
wide
range
of
electrocatalytic
processes.
A
vast
array
theoretical
and
computational
methods
have
been
developed
to
study
electrochemical
PCET.
These
can
be
used
calculate
redox
potentials
pKa
values
for
molecular
electrocatalysts,
proton-coupled
bond
dissociation
free
energies
PCET
at
metal
semiconductor
interfaces,
reorganization
associated
with
Periodic
density
functional
theory
also
compute
activation
perform
dynamics
simulations
interfaces.
Various
approaches
maintaining
constant
electrode
potential
electronic
structure
calculations
modeling
complex
interactions
the
electric
double
layer
(EDL)
developed.
Theoretical
formulations
both
homogeneous
heterogeneous
spanning
adiabatic,
nonadiabatic,
solvent-controlled
regimes
provide
analytical
expressions
rate
constants
current
densities
as
functions
applied
potential.
The
quantum
mechanical
treatment
proton
inclusion
excited
vibronic
states
shown
critical
describing
experimental
data,
such
Tafel
slopes
potential-dependent
kinetic
isotope
effects.
calculated
input
microkinetic
models
voltammogram
elucidate
Nature,
Journal Year:
2023,
Volume and Issue:
619(7970), P. 506 - 513
Published: June 28, 2023
Abstract
The
chemical
activation
of
water
would
allow
this
earth-abundant
resource
to
be
transferred
into
value-added
compounds,
and
is
a
topic
keen
interest
in
energy
research
1,2
.
Here,
we
demonstrate
with
photocatalytic
phosphine-mediated
radical
process
under
mild
conditions.
This
reaction
generates
metal-free
PR
3
–H
2
O
cation
intermediate,
which
both
hydrogen
atoms
are
used
the
subsequent
transformation
through
sequential
heterolytic
(H
+
)
homolytic
•
cleavage
two
O–H
bonds.
–OH
intermediate
provides
an
ideal
platform
that
mimics
reactivity
‘free’
atom,
can
directly
closed-shell
π
systems,
such
as
activated
alkenes,
unactivated
naphthalenes
quinoline
derivatives.
resulting
H
adduct
C
radicals
eventually
reduced
by
thiol
co-catalyst,
leading
overall
transfer
hydrogenation
system,
ending
up
product.
thermodynamic
driving
force
strong
P=O
bond
formed
phosphine
oxide
by-product.
Experimental
mechanistic
studies
density
functional
theory
calculations
support
atom
key
step
process.
Advanced Materials,
Journal Year:
2022,
Volume and Issue:
35(11)
Published: Dec. 15, 2022
Organic
electronics
has
made
great
progress
in
the
past
decades,
which
is
inseparable
from
innovative
development
of
organic
electronic
devices
and
diversity
semiconductor
materials.
It
worth
mentioning
that
both
these
advances
are
inextricably
linked
to
high-performance
materials,
especially
representative
n-type
small-molecule
materials
with
high
electron
mobilities.
The
small
molecules
have
advantages
simple
synthesis
process,
strong
intermolecular
stacking,
tunable
molecular
structure,
easy
functionalize
structures.
Furthermore,
a
remarkable
important
component
for
constructing
complementary
logic
circuits
p-n
heterojunction
Therefore,
semiconductors
play
an
extremely
role
field
basis
industrialization
functional
devices.
This
review
focuses
on
modification
strategies
mobility
at
level,
discusses
detail
applications
field-effect
transistors,
light-emitting
photodetectors,
gas
sensors.
Science,
Journal Year:
2023,
Volume and Issue:
381(6656), P. 444 - 451
Published: July 27, 2023
Developing
synthetically
useful
enzymatic
reactions
that
are
not
known
in
biochemistry
and
organic
chemistry
is
an
important
challenge
biocatalysis.
Through
the
synergistic
merger
of
photoredox
catalysis
pyridoxal
5'-phosphate
(PLP)
biocatalysis,
we
developed
a
radical
biocatalysis
approach
to
prepare
valuable
noncanonical
amino
acids,
including
those
bearing
stereochemical
dyad
or
triad,
without
need
for
protecting
groups.
Using
engineered
PLP
enzymes,
either
enantiomeric
product
could
be
produced
biocatalyst-controlled
fashion.
Synergistic
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(36), P. 16219 - 16231
Published: Sept. 2, 2022
The
odyssey
of
photochemistry
is
accompanied
by
the
journey
to
manipulate
"electrons"
and
"protons"
in
time,
space,
energy.
Over
past
decades,
single-electron
(1e-)
photochemical
transformations
have
brought
marvelous
achievements.
However,
as
each
photon
absorption
typically
generates
only
one
exciton
pair,
it
exponentially
challenging
accomplish
multielectron
proton
transformations.
multistep
differences
thermodynamics
kinetics
urgently
require
us
optimize
light
harvesting,
expedite
consecutive
electron
transfer,
interaction
catalysts
with
substrates,
coordinate
transfer
furnish
selective
bond
formations.
Tandem
catalysis
enables
orchestrating
different
events
catalytic
from
subpicoseconds
seconds,
which
facilitates
redox
chemistries
brings
consecutive,
value-added
reactivities.
Joint
efforts
molecular
material
design,
mechanistic
understanding,
theoretical
modeling
will
bring
synthetic
opportunities
for
fuels,
fertilizers,
chemicals
enhanced
versatility,
efficiency,
selectivity,
scalability,
thus
taking
better
advantage
photons
(i.e.,
sunlight)
our
sustainable
society.
European Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
2022(34)
Published: May 13, 2022
Abstract
The
opportunity
to
activate
C(sp
3
)−H
bonds
via
homolytic
cleavage
by
means
of
halogen
radicals
has
long
been
disregarded
in
synthetic
endeavors
due
the
unpredictable
selectivity.
Nowadays,
photocatalysis
established
itself
as
a
method
choice
for
generation
such
reactive
intermediates
under
mild
conditions.
This
Minireview
collects
recent
examples
showcasing
how
photocatalytic
manifolds
have
used
tame
aggressive
Hydrogen
Atom
Transfer
(HAT)
purposes.
In
last
section
this
work,
we
address
site‐selectivity
issues
posed
methodology
and
show
it
can
be
guided
through
judicious
reaction
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(13), P. 7050 - 7064
Published: March 21, 2023
This
Perspective
argues
that
most
redox
reactions
of
materials
at
an
interface
with
a
protic
solution
involve
net
proton-coupled
electron
transfer
(PCET)
(or
other
cation-coupled
ET).
view
contrasts
the
traditional
electron-transfer-focused
semiconductors,
but
processes
metal
surfaces
are
often
described
as
PCET.
Taking
thermodynamic
perspective,
is
typically
accompanied
by
stoichiometric
proton,
much
chemistry
lithium-ion
batteries
involves
coupled
transfers
e-
and
Li+.
The
PCET
viewpoint
implicates
surface-H
bond
dissociation
free
energy
(BDFE)
preeminent
energetic
parameter
its
conceptual
equivalents,
electrochemical
ne-/nH+
potential
versus
reversible
hydrogen
electrode
(RHE)
hydrogenation,
ΔG°H.
These
parameters
capture
thermochemistry
interfaces
better
than
electronic
such
Fermi
energies,
chemical
potentials,
flat-band
or
band-edge
energies.
A
unified
picture
semiconductor
presented.
Exceptions,
limitations,
implications,
future
directions
motivated
this
approach
described.
