Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 9, 2024
Abstract
Development
of
mild,
robust
and
metal‐free
catalytic
approach
for
the
hydrosilylation
alkenes
is
critical
to
advancement
modern
organosilicon
chemistry
given
their
powerful
capacity
in
construction
various
C−Si
bonds.
Herein,
we
wish
disclose
a
visible
light‐triggered
organophotocatalytic
strategy,
which
proceeds
via
triplet
energy
transfer
(
EnT
)‐enabled
radical
chain
pathway.
Notably,
this
redox‐neutral
protocol
capable
accommodating
broad
spectrum
electron‐deficient
‐rich
with
excellent
functional
group
compatibility.
Electron‐deficient
are
more
reactive
reaction
could
be
finished
within
couple
minutes
even
PBS
solution
extremely
low
concentration,
suggests
its
click‐like
potential
organic
synthesis.
The
preparative
power
transformations
has
been
further
highlighted
number
complex
settings,
including
late‐stage
functionalization
scale‐up
experiments.
Furthermore,
although
only
highly
(TMS)
3
SiH
suitable
hydrosilane
substrate,
our
studies
revealed
great
reactivity
versatility
Si−
diverse
Si−Si
bond
cleavage‐based
transformations,
enabling
rapid
introduction
groups
facile
valuable
quaternary
silicon
architectures.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(9), P. 6667 - 6673
Published: April 16, 2024
C–O
axially
chiral
diaryl
ethers
play
important
roles
in
natural
products
and
bioactive
molecules,
but
because
of
the
low
rotational
barrier
strict
steric
hindrance
requirements,
catalytic
asymmetric
construction
still
remains
a
challenge.
Herein,
we
devised
strategy
employing
achiral
azlactone
for
desymmetrization
prochiral
diamines
under
catalysis
phosphoric
acid.
The
targeted
were
obtained
very
good
yields
(up
to
98%)
high
enantioselectivities
>99.5:0.5
er).
synthetic
utility
was
demonstrated
through
large-scale
reaction
transformations
products.
Moreover,
DFT
calculations
conducted
probe
origins
enantioselectivity.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(14), P. 8161 - 8203
Published: Jan. 1, 2024
The
strategic
installation
of
the
“magic
methyl”
group
has
become
highly
desirable
for
drug
discovery.
This
review
summarized
recent
photochemical
and
electrochemical
strategies
in
installing
methyl
group.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 11, 2025
An
EnT-mediated
C3-N-heteroarylation
of
2-aryl
quinoxalines
via
decarboxylative
radical-radical
cross-coupling
(C(sp2)-C(sp2))
with
oxime
esters
is
presented.
Upon
photoactivation,
the
triplet
energy
photocatalyst
transferred
to
both
reacting
partners
(oxime
ester
and
2-phenylquinoxaline).
The
excited
undergoes
fragmentation
a
C-centered
N-heteroaryl
radical
an
N-centered
imine
radical.
former
attacks
C3
site
quinoxaline
diradical,
while
latter
acts
as
hydrogen
atom
abstractor
(HAA).
Computational
studies
revealed
that
C-C
bond
formation
heteroaryl
energetically
more
favorable
than
C-N
formation.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 18, 2025
Ligand-to-metal
charge
transfer
(LMCT)
excitation
has
emerged
as
a
potent
strategy
for
the
selective
generation
of
heteroatom-centered
radicals,
yet
its
full
potential
in
modulating
open-shell
radical
pathways
remains
underexplored.
Here,
we
present
photocatalytic
methylative
cross-coupling
reaction
that
capitalizes
on
synergistic
interplay
between
LMCT
and
Ni
catalysis,
enabling
use
tert-butanol
an
efficient
benign
methylating
reagent.
The
electron-deficient
ligand
2,6-ditrifluoromethyl
benzoate
facilitates
Ce(IV)-mediated
bond
scission
tert-butanol,
generating
methyl
is
subsequently
captured
by
catalytic
cycle
to
form
C-CH3
bonds.
Under
mild
conditions,
this
affords
methylation
sp3
carbons
adjacent
carbonyls
sp2
centers,
demonstrating
broad
functional
group
tolerance
applicability
late-stage
functionalization
bioactive
molecules.
Additionally,
trideuteromethylative
coupling
can
be
facilely
achieved
using
commercial
tert-butanol-d10.
This
approach
circumvents
need
traditional
tert-butoxy
precursors,
such
peroxides,
while
strategically
pathway
favor
β-scission
suppress
unwanted
formation
solution.
Mechanistic
studies
reveal
plays
crucial
role
facilitating
generation,
supporting
concerted
Ce-OR
β-C-C
homolysis
mechanism,
further
evidenced
modulation
regioselectivity
alkoxy
radical-mediated
β-scission.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(72)
Published: Oct. 6, 2023
Direct
C-H
methylation
is
a
highly
valuable
approach
for
introducing
methyl
groups
into
organic
molecules,
particularly
in
pharmaceutical
chemistry.
Among
the
various
methodologies
available,
photo-induced
stands
out
as
an
exceptional
choice
due
to
its
mild
reaction
conditions,
energy
efficiency,
and
compatibility
with
functional
groups.
This
article
offers
comprehensive
review
of
photochemical
strategies
employed
direct
selective
C(sp3
)-H,
C(sp2
C(sp)-H
bonds
molecules.
The
discussed
encompass
transition-metal-based
photocatalysis,
organophotocatalysis,
well
other
metal-free
approaches,
including
electron
donor-acceptor
(EDA)-enabled
transformations.
Importantly,
wide
range
easily
accessible
agents
such
tert-butyl
peroxide,
methanol,
DMSO,
ether,
TsOMe,
N-(acetoxy)phthalimide,
acetic
acid,
halides,
even
methane
can
serve
effective
methylating
reagents
modifying
diverse
targets.
These
advancements
are
anticipated
drive
further
progress
fields
synthesis,
development,
opening
up
exciting
avenues
creating
novel
molecules
discovering
new
drug
compounds.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(13)
Published: Jan. 22, 2024
Abstract
The
burgeoning
field
of
semiconductor‐mediated
organic
conversion
is
paramount
significance,
with
zinc
indium
sulfide
(ZnIn
2
S
4
)
emerging
as
a
standout
candidate
owing
to
its
benign
nature,
optimal
bandgap,
extensive
light
absorption
spectrum,
remarkable
physicochemical
properties,
and
straightforward
synthesis.
This
review
examines
the
latest
breakthroughs
trajectory
ZnIn
‐based
photocatalysts
in
realm
selective
transformation.
We
start
distinct
overview
intrinsic
physical
attributes
underlying
mechanisms
driving
efficacy
photocatalytic
transformations.
Subsequently,
preparation
methods
are
summarized.
main
focus
state‐of‐the‐art
application
various
photocatalysts,
such
redox
reactions,
construction
C−C,
C−S
S−S
bonds,
cleavage
C−O,
C=C
bonds.
In
conclusion
part,
we
provide
our
perspectives
on
prospective
advancements
remaining
challenges
that
lie
ahead
optimization
ultimate
goal
enhancing
their
for
diverse
array
photosynthetic
applications.
It
anticipated
inspire
strategic
engineering
other
semiconductor‐based
artificial
photosynthesis
reactions.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(34), P. 13650 - 13658
Published: Jan. 1, 2024
Energy
transfer
(EnT)
photocatalysis
holds
the
potential
to
revolutionize
synthetic
chemistry,
unlocking
excited-state
reactivity
of
non-chromophoric
compounds
