Nature Chemistry,
Journal Year:
2024,
Volume and Issue:
16(7), P. 1151 - 1159
Published: March 18, 2024
Abstract
Photoredox
catalysis
relies
on
light-induced
electron
transfer
leading
to
a
radical
pair
comprising
an
oxidized
donor
and
reduced
acceptor
in
solvent
cage.
For
productive
onward
reaction
occur,
the
must
escape
from
that
cage
before
they
undergo
spontaneous
reverse
transfer.
Here
we
show
decisive
role
plays
three
benchmark
photocatalytic
reactions,
namely,
aerobic
hydroxylation,
reductive
debromination
aza-Henry
reaction.
Using
ruthenium(II)-
chromium(III)-based
photocatalysts,
which
provide
inherently
different
quantum
yields,
determined
quantitative
correlations
between
rates
of
photoredox
product
formation
yields.
These
findings
can
be
largely
rationalized
within
framework
Marcus
theory
for
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(18), P. 7988 - 7994
Published: April 27, 2022
Saturated
bicycles
are
becoming
ever
more
important
in
the
design
and
development
of
new
pharmaceuticals.
Here
a
strategy
for
synthesis
bicyclo[2.1.1]hexanes
is
described.
These
significant
because
they
have
defined
exit
vectors,
yet
many
substitution
patterns
underexplored
as
building
blocks.
The
process
involves
sensitization
bicyclo[1.1.0]butane
followed
by
cycloaddition
with
an
alkene.
scope
mechanistic
details
method
discussed.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(9), P. 5225 - 5261
Published: Jan. 20, 2023
Because
sunlight
is
the
most
abundant
energy
source
on
earth,
it
has
huge
potential
for
practical
applications
ranging
from
sustainable
supply
to
light
driven
chemistry.
From
a
chemical
perspective,
excited
states
generated
by
make
thermodynamically
uphill
reactions
possible,
which
forms
basis
storage
into
fuels.
In
addition,
with
light,
open-shell
species
can
be
open
up
new
reaction
pathways
in
organic
synthesis.
Crucial
are
photosensitizers,
absorb
and
transfer
substrates
various
mechanisms,
processes
that
highly
depend
distance
between
molecules
involved.
Supramolecular
coordination
cages
well
studied
synthetically
accessible
vessels
single
cavities
guest
binding,
ensuring
close
proximity
of
different
components.
Due
high
modularity
their
size,
shape,
nature
metal
centers
ligands,
ideal
platforms
exploit
preorganization
photocatalysis.
Herein
we
focus
application
supramolecular
photocatalysis
artificial
photosynthesis
photo(redox)
catalysis.
Finally,
brief
overview
immobilization
strategies
provides
tools
implementing
devices.
This
review
inspiration
future
design
photocatalytic
host-guest
systems
producing
solar
fuels
complex
molecules.
Advanced Materials,
Journal Year:
2022,
Volume and Issue:
35(24)
Published: Dec. 23, 2022
Abstract
Organic
photochemistry
is
intensely
developed
in
the
1980s,
which
nature
of
excited
electronic
states
and
energy
electron
transfer
processes
are
thoroughly
studied
finally
well‐understood.
This
knowledge
from
molecular
organic
can
be
transferred
to
design
covalent
frameworks
(COFs)
as
active
visible‐light
photocatalysts.
COFs
constitute
a
new
class
crystalline
porous
materials
with
substantial
application
potentials.
Featured
outstanding
structural
tunability,
large
porosity,
high
surface
area,
excellent
stability,
unique
photoelectronic
properties,
potential
candidates
various
research
areas
(e.g.,
photocatalysis).
review
aims
provide
state‐of‐the‐art
insights
into
COF
photocatalysts
(pristine,
functionalized,
hybrid
COFs)
for
transformations.
The
catalytic
reaction
mechanism
COF‐based
influence
dimensionality
crystallinity
on
heterogenous
photocatalysis
performance
also
discussed,
followed
by
perspectives
prospects
main
challenges
opportunities
future
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(3), P. 1068 - 1089
Published: Jan. 1, 2024
Leveraging
light
energy
to
expose
the
‘dark’
reactive
states
describes
whole
essence
of
triplet–triplet
transfer.
This
offers
an
impressive
opportunity
conduct
a
multitude
diverse
reactions
and
access
sought-after
molecular
motifs.
Accounts of Chemical Research,
Journal Year:
2022,
Volume and Issue:
55(17), P. 2510 - 2525
Published: Aug. 9, 2022
Exploring
the
enormous
chemical
space
through
an
expedient
building-up
of
molecular
diversity
is
important
goal
organic
chemistry.
The
development
synthetic
methods
toward
molecules
with
unprecedented
structural
motifs
lays
foundation
for
wide
applications
ranging
from
pharmaceutical
chemistry
to
materials
science.
In
this
regard,
dearomatization
arenes
has
been
recognized
as
a
unique
strategy
since
it
provides
novel
retrosynthetic
disconnections
various
spiro
or
fused
polycyclic
increased
saturation
and
stereoisomerism.
However,
inherent
thermodynamic
challenges
are
associated
processes.
disruption
aromaticity
arene
substrates
usually
requires
large
energy
inputs,
which
makes
harsh
conditions
necessary
many
ground-state
reactions.
Therefore,
further
expansion
scope
reactions
remains
major
problem
not
fully
solved
in
chemistry.The
past
decade
witnessed
tremendous
progress
on
photocatalytic
under
visible
light.
Particularly,
via
transfer
mechanism
have
unlocked
new
opportunities
Mediated
by
appropriately
chosen
photosensitizers,
aromatic
can
be
excited.
This
kind
precise
input
might
make
feasible
some
that
otherwise
unfavorable
thermal
because
significant
increases
substrates.
Nevertheless,
lifetimes
key
intermediates
energy-transfer-enabled
reactions,
such
excited-state
aromatics
downstream
biradical
species,
quite
short.
How
regulate
reactivities
these
transient
achieve
exclusive
selectivity
certain
reaction
pathway
among
possibilities
crucial
issue
addressed.Since
2019,
our
group
reported
series
visible-light-induced
dearomative
cycloaddition
indole
pyrrole
derivatives.
It
was
found
units
excited
irradiation
light
presence
suitable
photosensitizer.
These
readily
undergo
[m
+
n]
tethered
unsaturated
functionalities
including
alkenes,
alkynes,
N-alkoxy
oximes,
(hetero)arenes,
vinylcyclopropanes.
yield
indolines
pyrrolines
highly
strained
small-
and/or
medium-sized
rings
embedded,
possess
bridge-
cagelike
topologies.
Systematic
mechanistic
studies
confirmed
involvement
process.
Density
functional
theory
(DFT)
calculations
revealed
correlation
between
substrate
structure
excitation
efficiency,
accelerated
optimization
parameters.
Meanwhile,
DFT
demonstrated
competition
kinetically
thermodynamically
controlled
pathways
open-shell
singlet
intermediates,
allowed
complete
switches
[2
2]
1,5-hydrogen
atom
oximes
[4
naphthalene.
Furthermore,
ab
initio
dynamics
(AIMD)
simulations
uncovered
post-spin
crossing
dynamic
effects,
determine
regioselectivity
recombination
step
pyrrole-derived
vinylcyclopropanes.An
increasing
number
scientists
joined
research
contributed
more
elegant
examples
area.
mechanism,
although
still
its
infancy,
exhibited
great
potential
synthesis
hardly
accessed
other
methods.
We
believe
future
will
push
boundary
find
related
disciplines.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(14), P. 12308 - 12369
Published: May 20, 2022
Transition
metal
catalysis
is
of
utmost
importance
for
the
development
sustainable
processes
in
academia
and
industry.
The
activity
selectivity
complexes
are
typically
result
interplay
between
ligand
properties.
As
can
be
chemically
altered,
a
large
research
focus
has
been
on
development.
More
recently,
it
recognized
that
further
control
over
achieved
by
using
“second
coordination
sphere”,
which
seen
as
region
beyond
direct
sphere
center.
Hydrogen
bonds
appear
to
very
useful
interactions
this
context
they
have
sufficient
strength
directionality
exert
second
sphere,
yet
hydrogen
dynamic,
allowing
fast
turnover.
In
review
we
highlighted
several
key
features
bonding
summarized
use
program
sphere.
Such
bridging
two
ligands
coordinated
center
effectively
lead
supramolecular
bidentate
ligands.
addition,
used
preorganize
substrate
Both
strategies
catalysts
with
superior
properties
variety
catalyzed
transformations,
including
(asymmetric)
hydrogenation,
hydroformylation,
C–H
activation,
oxidation,
radical-type
photochemical
reactions.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(44), P. 20207 - 20213
Published: Oct. 27, 2022
Synthesis
of
bicyclic
scaffolds
has
attracted
growing
interest
because
they
are
high
importance
in
modern
pharmaceutical
development.
Here
we
report
a
strategy
to
access
polysubstituted
2-oxabicyclo[2.1.1]hexanes
single
operation
from
readily
accessible
benzoylformate
esters
and
bicyclo[1.1.0]butanes
via
visible-light-induced
triplet
energy
transfer
catalysis.
The
process
is
proposed
involve
formal
[2π
+
2σ]
photocycloaddition/backbone
C-H
abstraction/aryl
group
migration
sequence.
A
diverse
range
(hetero)aryl
groups
successfully
underwent
the
backbone
(C2)
position
provide
previously
inaccessible
molecules,
ester
product
can
serve
as
handle
for
downstream
manipulation,
thus
offering
opportunities
rapidly
build
up
molecular
complexity
new
sp3-rich
chemical
space.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(22), P. 12324 - 12332
Published: May 26, 2023
Dearomative
photocycloadditions
are
valuable
chemical
transformations,
serving
as
an
efficient
platform
to
create
three-dimensional
molecular
complexity.
However,
the
photolability
of
original
addition
product
especially
within
context
ortho
cycloadditions
often
causes
undesired
consecutive
rearrangements,
rendering
these
cycloadducts
elusive.
Herein,
we
report
ortho-selective
intermolecular
photocycloaddition
bicyclic
aza-arenes
including
(iso)quinolines,
quinazolines,
and
quinoxalines
by
utilizing
a
strain-release
approach.
With
bicyclo[1.1.0]butanes
coupling
partners,
this
dearomative
[2π
+
2σ]
cycloaddition
enables
straightforward
construction
C(sp3)-rich
bicyclo[2.1.1]hexanes
directly
connected
N-heteroarenes.
Photophysical
experiments
DFT
calculations
revealed
origin
selectivity
indicate
that,
in
originally
proposed
energy
transfer
or
direct
excitation
pathways,
chain
reaction
mechanism
is
operative
depending
on
conditions.
