Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(26)
Published: April 20, 2024
Abstract
Photoinduced
Pd‐catalyzed
bisfunctionalization
of
butadienes
with
a
readily
available
organic
halide
and
nucleophile
represents
an
emerging
attractive
method
to
assemble
versatile
alkenes
bearing
various
functional
groups
at
the
allylic
position.
However,
enantiocontrol
and/or
diastereocontrol
in
C−C
or
C−X
bond‐formation
step
have
not
been
solved
due
open‐shell
process.
Herein,
we
present
cascade
asymmetric
dearomatization
reaction
indoles
via
photoexcited
1,2‐biscarbonfunctionalization
1,3‐butadienes,
wherein
control
on
both
electrophile
part
is
achieved
for
first
time
photoinduced
butadienes.
This
delivers
structurally
novel
chiral
spiroindolenines
two
contiguous
stereogenic
centers
high
diastereomeric
ratios
(up
>20
:
1
dr)
good
excellent
enantiomeric
97
3
er).
Experimental
computational
studies
mechanism
confirmed
radical
pathway
involving
excited‐state
palladium
catalysis.
The
alignment
non‐covalent
interactions
between
substrate
catalyst
were
found
be
essential
stereocontrol.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(9)
Published: Nov. 14, 2023
Visible
light-induced
Pd
catalysis
has
emerged
as
a
promising
subfield
of
photocatalysis.
The
hybrid
nature
radical
species
enabled
wide
array
radical-based
transformations
otherwise
challenging
or
unknown
via
conventional
chemistry.
In
parallel
to
the
ongoing
pursuit
alternative,
readily
available
precursors,
notable
discoveries
have
demonstrated
that
photoexcitation
can
alter
not
only
oxidative
addition
but
also
other
elementary
steps.
This
Minireview
highlights
recent
progress
in
this
area.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 4665 - 4680
Published: March 5, 2025
Transition
metal
catalysis
is
an
indispensable
tool
for
organic
synthesis
that
has
been
harnessed,
modulated,
and
perfected
many
decades
by
careful
selection
of
centers
ligands,
giving
rise
to
synthetic
methods
with
unparalleled
efficiency
chemoselectivity.
Recent
developments
have
demonstrated
how
light
irradiation
can
also
be
recruited
as
a
powerful
dramatically
alter
the
outcome
catalytic
reactions,
providing
access
innovative
pathways
remarkable
potential.
In
this
context,
adoption
photochemical
conditions
mainstream
strategy
drive
reactions
unveiled
exciting
opportunities
exploit
rich
excited-state
framework
transition
metals
applications.
This
Perspective
examines
advances
in
application
complexes
standalone
photocatalysts,
exploiting
innate
reactivity
their
excited
states
beyond
common
use
photoredox
catalysts.
An
account
relevant
examples
dissected
provide
discussion
on
electronic
reorganization,
orbitals
involved,
associated
different
types
states.
analysis
aims
practitioners
fundamental
principles
guiding
strategies
understand,
design,
apply
light-activation
homogeneous
synthesis.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(26)
Published: April 20, 2024
Photoinduced
Pd-catalyzed
bisfunctionalization
of
butadienes
with
a
readily
available
organic
halide
and
nucleophile
represents
an
emerging
attractive
method
to
assemble
versatile
alkenes
bearing
various
functional
groups
at
the
allylic
position.
However,
enantiocontrol
and/or
diastereocontrol
in
C-C
or
C-X
bond-formation
step
have
not
been
solved
due
open-shell
process.
Herein,
we
present
cascade
asymmetric
dearomatization
reaction
indoles
via
photoexcited
1,2-biscarbonfunctionalization
1,3-butadienes,
wherein
control
on
both
electrophile
part
is
achieved
for
first
time
photoinduced
butadienes.
This
delivers
structurally
novel
chiral
spiroindolenines
two
contiguous
stereogenic
centers
high
diastereomeric
ratios
(up
>20
:
1
dr)
good
excellent
enantiomeric
97
3
er).
Experimental
computational
studies
mechanism
confirmed
radical
pathway
involving
excited-state
palladium
catalysis.
The
alignment
non-covalent
interactions
between
substrate
catalyst
were
found
be
essential
stereocontrol.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(47)
Published: Oct. 3, 2023
Abstract
Palladium
hydrides
are
traditionally
employed
in
hydrofunctionalization
(i.e.
monofunctionalization)
of
conjugated
dienes
and
enynes,
owning
to
its
facile
protic
hydropalladation
electron‐rich
(or
neutral)
unsaturated
bonds.
Herein,
we
report
a
mild
PdH‐catalyzed
difunctionalization
enynes.
This
protocol
is
enabled
by
the
chemoselectivity
switch
initial
step
achieved
visible
light
enhancement
hydricity
PdH
species.
method
allows
for
cascade
annulation
enynes
with
various
easily
available
abundant
substrates,
such
as
acrylic
acids,
amides,
Baylis–Hillman
adducts,
toward
wide
range
alkenyl
or
alkynyl
lactones,
lactams,
tetrahydrofurans.
also
provides
an
easy
access
complex
spiro‐fused
tricyclic
frameworks.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(46), P. 25098 - 25102
Published: Nov. 10, 2023
Olefins
are
widely
available
at
low
costs,
which
explains
the
usefulness
of
developing
new
methods
for
their
functionalization.
Here
we
report
a
simple
protocol
that
uses
photoredox
catalyst
and
an
inexpensive
thiol
to
stitch
together
two
olefins,
forming
C-C
bond.
Specifically,
electron-poor
olefin
is
reduced
by
generate,
upon
protonation,
carbon
radical,
then
captured
neutral
olefin.
This
intermolecular
cross-coupling
process
provides
tool
rapidly
synthesizing
sp3-dense
molecules
from
olefins
using
unconventional
disconnection.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(13)
Published: Jan. 19, 2024
Abstract
In
modern
organic
chemistry,
harnessing
the
power
of
multicomponent
radical
reactions
presents
both
significant
challenges
and
extraordinary
potential.
This
article
delves
into
this
scientific
frontier
by
addressing
critical
issue
controlling
selectivity
in
such
complex
processes.
We
introduce
a
novel
approach
that
revolves
around
reversible
addition
thiyl
radicals
to
multiple
bonds,
reshaping
landscape
reactions.
The
key
lies
intricate
interplay
between
reversibility
energy
landscapes
governing
C−C
bond
formation
thiol‐yne‐ene
developed
not
only
allows
prioritize
cascade,
dominating
over
alternative
reactions,
but
also
extends
scope
coupling
products
obtained
from
alkenes
alkynes
various
structures
electron
density
distributions,
regardless
their
relative
polarity
difference,
opening
doors
more
versatile
synthetic
possibilities.
present
study,
we
provide
powerful
tool
for
atom‐economical
C−S
formation,
paving
way
efficient
synthesis
molecules.
Carrying
out
our
experimental
computational
studies,
elucidated
fundamental
mechanisms
underlying
cascades,
knowledge
can
be
broadly
applied
field
chemistry.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 23, 2025
Herein,
aromaticity-driven
thio(seleno)ester
group
transfer
from
novel
1,4-dihydropyridine
thio(seleno)esters
to
alkene
feedstocks
is
disclosed
by
merging
palladium
and
photoredox
catalysis.
In
this
process,
photoactivation
of
dihydropyridine
integrated
with
regioselective
hydrometalation
alkenes,
avoiding
photoinduced
Pd-C
bond
homolysis
organopalladium
intermediates.
Additionally,
a
hydroselenocarbonylation
an
accomplished
for
the
first
time
using
bench-stable
selenoester
reagent.
The
activation
mode
thioesters
has
been
illustrated
detailed
mechanistic
studies,
spectroscopic
analysis,
intermediate
trapping,
isotope
labeling
experiments.
Accounts of Chemical Research,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 26, 2025
ConspectusThe
past
decade
has
witnessed
significant
advancements
of
visible-light-induced
photocatalysis,
establishing
it
as
a
powerful
and
versatile
tool
in
organic
synthesis.
The
major
focus
this
field
centered
on
the
development
methodologies
that
either
rely
solely
photocatalysts
or
combine
photocatalysis
with
other
catalytic
methods,
such
transition
metal
catalysis,
to
address
broader
more
diverse
array
transformations.
Within
rapidly
evolving
area,
subfield
we
refer
garnered
attention
due
its
growing
impact
mechanistic
uniqueness.
A
distinguishing
feature
is
dual
functionality
single
complex,
which
not
only
acts
photocatalyst
initiate
photochemical
processes
but
also
functions
traditional
catalyst,
facilitating
key
bond-breaking
bond-forming
events.
As
such,
an
exogenous
required
photocatalysis.
However,
implications
harnessing
both
excited-
ground-state
reactivities
complex
can
extend
beyond
simplification.
One
most
compelling
aspects
area
photoexcited
complexes
exhibit
unique
inaccessible
through
conventional
thermal
photocatalytic
approaches.
These
distinct
be
leveraged
accomplish
novel
transformations
by
engaging
entirely
different
substrate
pool
unlocking
new
known
substrates.In
2016,
our
group
pioneered
use
phosphine-ligated
palladium
catalysts
upon
visible-light
irradiation
engage
substrates
radical
reactions.
In
initial
discovery,
showed
photoexcitation
redirect
well-established
oxidative
addition
Pd(0)
into
aryl
iodides
toward
unprecedented
process,
generating
hybrid
Pd(I)
species.
We
subsequently
extended
strategy
formation
alkyl
radicals
from
halides.
reactive
intermediates
have
been
harnessed
wide
variety
transformations,
including
desaturation,
Heck
reactions,
alkene
difunctionalization
cascades,
among
others.Seeking
further
expand
avenue,
achieved
first
example
asymmetric
context
allylic
C–H
amination,
where
catalyst
now
plays
triple
duty
additionally
controlling
stereochemical
outcome
reaction.
parallel
reaction
established
diazo
compounds,
strained
molecules,
electron-deficient
alkenes
serve
precursors
halides
redox-active
esters.
Notably,
engagement
made
possible
photoinduced
hydricity
enhancement
Pd–H
species,
representing
mode
reactivity.This
Account
presents
discovery
organized
type
explored.
Given
rapid
progress
field,
anticipate
will
provide
readers
guiding
principles
inspiration
for
designing
developing
efficient