Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(45)
Published: Sept. 26, 2023
Herein,
we
report
a
photoinduced
approach
for
hydroarylation
of
unactivated
olefins
using
4-hydroxycoumarins
as
the
arylating
reagent.
Key
to
success
this
reaction
is
conversion
nucleophilic
into
electrophilic
carbon
radicals
via
photocatalytic
arene
oxidation,
which
not
only
circumvents
polarity-mismatch
issue
encountered
under
ionic
conditions
but
also
accommodates
broad
substrate
scope
and
inhibits
side
reactions
that
were
previously
observed.
Moreover,
divergent
reactivity
was
achieved
by
changing
photocatalyst,
enabling
subsequent
[2+2]
cycloaddition
deliver
cyclobutane-fused
pentacyclic
products
are
otherwise
challenging
access
in
high
yields
with
diastereoselectivity.
Mechanistic
studies
have
elucidated
mechanism
origin
reactivity.
Nature Synthesis,
Journal Year:
2024,
Volume and Issue:
3(6), P. 707 - 714
Published: March 11, 2024
Abstract
Spontaneous
chemical
reactions
proceed
energetically
downhill
to
either
a
local
or
global
minimum,
limiting
possible
transformations
those
that
are
exergonic.
Endergonic
do
not
spontaneously
and
require
an
input
of
energy.
Light
has
been
used
drive
number
deracemizations
thermodynamically
unfavourable
bond-forming
reactions,
but
is
restricted
substrates
can
absorb,
directly
indirectly,
energy
provided
by
photons.
In
contrast,
anabolism
involves
uphill
powered
fuels.
Here
we
report
on
the
transduction
from
artificial
fuel
Diels–Alder
reaction.
Carboxylic
acid
catalysed
carbodiimide-to-urea
formation
chemically
orthogonal
reaction
diene
dienophile,
transiently
brings
functional
groups
into
close
proximity,
causing
otherwise
prohibited
cycloaddition
in
modest
yield
(15%
after
two
fuelling
cycles)
with
high
levels
regio-
(>99%)
stereoselectivity
(92:8
exo
:
endo
).
Kinetic
asymmetry
cycle
ratchets
away
equilibrium
distribution
Diels–Alder:retro-Diels–Alder
products.
The
driving
endergonic
occurs
through
ratchet
mechanism
(an
information
ratchet,
depending
synthetic
protocol),
reminiscent
how
molecular
machines
directionally
bias
motion.
Ratcheting
synthesis
potential
expand
chemistry
toolbox
terms
reactivity,
complexity
control.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(5), P. 2895 - 2900
Published: Jan. 26, 2024
Performing
abiotic
synthetic
transformations
in
live
cell
environments
represents
a
new,
promising
approach
to
interrogate
and
manipulate
biology
uncover
new
types
of
biomedical
tools.
We
now
found
that
photocatalytic
bond-forming
reactions
can
be
added
the
toolbox
bioorthogonal
chemistry.
Specifically,
we
demonstrate
exogenous
styryl
aryl
azides
converted
into
indoles
inside
living
mammalian
cells
under
conditions.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
57(9), P. 1360 - 1371
Published: April 26, 2024
ConspectusNonradiative
processes
with
the
determined
role
in
excited-state
energy
conversion,
such
as
internal
conversion
(IC),
vibrational
relaxation
(VR),
intersystem
crossing
(ISC),
and
or
electron
transfer
(ET
eT),
have
exerted
a
crucial
effect
on
biological
functions
nature.
Inspired
by
these,
nonradiative
process
manipulation
has
been
extensively
utilized
to
develop
organic
functional
materials
fields
of
biomedicine.
Therefore,
comprehensive
knowledge
effective
sophisticated
for
achieving
high-efficiency
are
quintessential.
So
far,
many
strategies
focused
molecular
engineering
demonstrated
tremendous
potential
manipulating
tailor
conversion.
Besides,
aggregation
considerably
affects
due
their
ultrasensitivity,
thus
providing
us
another
essential
approach
processes,
famous
aggregation-induced
emission.
However,
weak
interactions
established
upon
aggregation,
namely,
microenvironment
(AME),
possess
hierarchical,
dynamic,
systemic
characteristics
extremely
complicated
elucidate.
Revealing
relationship
between
AME
employing
it
customize
would
greatly
promote
advanced
utilization,
biomedicine,
etc.,
but
remain
huge
challenge.
Our
group
devoted
much
effort
this
goal.In
Account,
we
focus
our
recent
developments
based
AME.
First,
provide
insight
into
terms
its
steric
electronic
regulation,
illustrating
possibility
through
modulation.
Second,
distinct
enhanced
is
crystallization
heterogeneous
polymerization
conduct
crystallization-induced
reversal
from
dark
bright
excited
states
dynamic
hardening-triggered
suppression
highly
efficient
luminescence.
Meanwhile,
promoting
ISC
stabilizing
triplet
state
also
manipulated
crystal
polymer
matrix
induce
room-temperature
phosphorescence.
Furthermore,
employed
exploit
photothermy
photosensitization
reviewed.
For
photothermal
besides
weakened
promoted
motions,
new
strategy
involving
introduction
diradicals
narrow
band
gap
enhance
intermolecular
put
forward
facilitate
IC
VR
photosensitization,
both
rigid
regulation
electron-rich
ISC,
ET,
eT
superior
photosensitization.
Finally,
explore
existing
challenges
future
directions
modulation
customized
We
hope
that
Account
will
be
wide
interest
readers
different
disciplines.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(34), P. 24105 - 24113
Published: Aug. 15, 2024
The
quest
for
sustainable
strategies
in
molecular
synthesis
has
spurred
the
emergence
of
photocatalysis
as
a
particularly
powerful
technique.
In
recent
years,
application
this
context
greatly
promoted
development
asymmetric
catalysis.
Despite
impressive
advances,
enantioselective
photoinduced
strong
arene
C-H
activations
by
cobalt
catalysis
remain
unexplored.
Herein,
we
report
strategy
that
merges
organic
photoredox
and
cobalt-catalyzed
activation,
enabling
regio-
stereoselective
dual
functionalization
indoles
an
fashion.
Thereby,
assembly
various
chiral
indolo[2,3-
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Feb. 27, 2025
In
nature,
plants
convert
solar
energy
into
chemical
via
water
oxidation.
Inspired
by
natural
photosynthesis,
artificial
photosynthesis
has
been
gaining
increasing
interest
in
the
field
of
sustainability/green
science
and
technology
as
a
non-natural
thermodynamically
endergonic
(ΔG°
>
0,
uphill)
solar-energy-driven
reaction
that
uses
an
electron
donor
source
material.
Among
artificial-photosynthesis
processes,
inorganic-synthesis
reactions
oxidation,
including
splitting
CO2-to-fuel
conversion,
have
attracting
much
attention.
contrast,
synthesis
high-value
functionalized
organic
compounds
which
we
termed
directed
toward
(APOS),
remains
great
challenge.
Herein,
report
synthetically
pioneering
meaningful
strategy
APOS,
where
carbohydroxylation
C
=
double
bonds
is
accomplished
three-component
coupling
with
H2
evolution
using
dual
functions
semiconductor
photocatalysts,
i.e.,
silver-loaded
titanium
dioxide
(Ag/TiO2)
rhodium–chromium–cobalt-loaded
aluminum-doped
strontium
titanate
(RhCrCo/SrTiO3:Al).
Emulating
concept
long
focus
chemists
effort
to
harness
light
Here,
authors
present
photosynthetic
system
can
functionalize
styrenes
C–H
activation
splitting.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(13), P. 1583 - 1588
Published: Feb. 14, 2023
Comprehensive
Summary
A
new
electrochemical
strategy
for
the
atom
transfer
radical
addition
(ATRA)
of
polychloroalkanes
across
olefins
has
been
realized
by
synergism
paired
electrolysis
and
halogen
bonding
activation.
Notably,
readily
accessible
4,4‐di‐
tert
‐butyl
bipyridine
(dtbpy),
acting
as
a
acceptor,
shifted
reduction
potential
C—Cl
bonds
positively
110
mV.
The
decreased
operating
leads
to
wide
substrate
scope
excellent
functional
group
compatibility.
diverse
array
terminal
internal
alkenes
such
(hetero)aryl
olefins,
unactive
aliphatic
natural
products
drugs‐derived
were
well
compatible.
