Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(32)
Published: May 24, 2024
Abstract
Radical‐involved
multicomponent
difunctionalization
of
1,3‐dienes
has
recently
emerged
as
a
promising
strategy
for
rapid
synthesis
valuable
allylic
compounds
in
one‐pot
operation.
However,
the
expansion
radical
scope
and
enantiocontrol
remain
two
major
challenges.
Herein,
we
describe
an
unprecedented
photoinduced
copper‐catalyzed
highly
enantioselective
three‐component
1,2‐azidooxygenation
with
readily
available
azidobenziodazolone
reagent
carboxylic
acids.
This
mild
protocol
exhibits
broad
substrate
scope,
high
functional
group
tolerance,
exceptional
control
over
chemo‐,
regio‐
enantioselectivity,
providing
practical
access
to
diverse
azidated
chiral
esters.
Mechanistic
studies
imply
that
copper
complex
is
implicated
bifunctional
catalyst
both
photoredox
catalyzed
azidyl
generation
C−O
cross‐coupling.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(8), P. 4373 - 4505
Published: March 19, 2021
This
Review
compiles
the
evolution,
mechanistic
understanding,
and
more
recent
advances
in
enantioselective
Pd-catalyzed
allylic
substitution
decarboxylative
oxidative
substitutions.
For
each
reaction,
catalytic
data,
as
well
examples
of
their
application
to
synthesis
complex
molecules,
are
collected.
Sections
which
we
discuss
key
aspects
for
high
selectivity
a
comparison
with
other
metals
(with
advantages
disadvantages)
also
included.
asymmetric
substitution,
data
grouped
according
type
nucleophile
employed.
Because
prominent
position
use
stabilized
carbon
nucleophiles
heteronucleophiles,
many
chiral
ligands
have
been
developed.
To
better
compare
results,
they
presented
by
ligand
types.
reactions
mainly
promoted
PHOX
or
Trost
ligands,
justifies
organizing
this
section
chronological
order.
results
used.
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 Science,
Journal Year:
2023,
Volume and Issue:
14(16), P. 4230 - 4247
Published: Jan. 1, 2023
This
review
explores
the
benefits
of
flow
chemistry
and
dispels
notion
that
it
is
a
mysterious
“black
box”,
demonstrating
how
can
push
boundaries
organic
synthesis
through
understanding
its
governing
principles.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(33), P. 13382 - 13392
Published: Aug. 10, 2021
The
construction
of
carbon–heteroatom
bonds
is
one
the
most
active
areas
research
in
organic
chemistry
because
function
molecules
often
derived
from
presence
heteroatoms.
Although
considerable
advances
have
recently
been
achieved
radical-involved
catalytic
asymmetric
C–N
bond
formation,
there
has
little
progress
corresponding
C–O
bond-forming
processes.
Here,
we
describe
a
photoinduced
copper-catalyzed
cross-coupling
readily
available
oxime
esters
and
1,3-dienes
to
generate
diversely
substituted
allylic
with
high
regio-
enantioselectivity
(>75
examples;
up
95%
ee).
reaction
proceeds
at
room
temperature
under
excitation
by
purple
light-emitting
diodes
(LEDs)
features
use
single,
earth-abundant
copper-based
chiral
catalyst
as
both
photoredox
for
radical
generation
source
induction
coupling.
Combined
experimental
density
functional
theory
(DFT)
computational
studies
suggest
formation
π-allylcopper
complexes
redox-active
bifunctional
reagents
through
radical–polar
crossover
process.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(42), P. 22956 - 22962
Published: Aug. 18, 2021
Abstract
Kharasch–Sosnovsky
reaction
is
one
of
the
most
powerful
methods
for
allylic
oxidation
alkenes.
However,
inherent
radical
mechanism
and
use
peroxides
as
both
oxidants
oxygen
nucleophiles
render
dearth
universal
catalytic
systems
highly
enantioselective
variants
limited
scope.
Herein,
an
alternative
to
asymmetric
that
utilized
a
chiral
copper
catalyst
purple‐LED
irradiation
enable
three‐component
coupling
1,3‐dienes,
oxime
esters,
carboxylic
acids
reported.
This
protocol
features
mild
conditions,
remarkable
scope
functional
group
tolerance
evidenced
by
>80
examples
utility
in
late‐stage
modification
pharmaceuticals
natural
products.
Detailed
mechanistic
studies
provide
evidences
radical‐based
pathway.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(14)
Published: Feb. 9, 2024
Abstract
A
visible‐light‐induced,
three‐component
palladium‐catalyzed
1,4‐aminoarylation
of
butadienes
with
readily
available
aryl
halides
and
aliphatic
amines
has
been
developed,
affording
allylamines
excellent
E
‐selectivity.
The
reaction
exhibits
exceptional
control
over
chemo‐,
regio‐,
stereoselectivity,
a
broad
substrate
scope,
high
functional
group
compatibility,
as
demonstrated
by
the
late‐stage
functionalization
bioactive
molecules.
Mechanistic
investigations
are
consistent
photoinduced
radical
Pd(0)‐Pd(I)‐Pd(II)‐Pd(0)
Heck‐Tsuji–Trost
allylation
cascade.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(5), P. 3725 - 3732
Published: Feb. 21, 2024
The
chiral
allylic
sulfonylated
group
is
a
unique
structural
motif
embedded
in
range
of
natural
products
and
pharmaceuticals.
Notably,
the
synthesis
structurally
diverse
derivatives
via
alkylsulfonylation
1,3-dienes
remains
underexplored
because
its
inherent
challenges
stereocontrol
regioselectivity.
Herein,
photoinduced,
palladium-catalyzed
enantioselective
1,2-alkylsulfonylation
conjugated
described.
A
wide
variety
alkyl
bromides,
1,3-dienes,
sodium
sulfinates
could
be
facilely
coupled
to
generate
value-added
with
high
enantioselectivity.
Finally,
utility
this
difunctionalization
protocol
was
demonstrated
pharmaceutical
analogue
synthesis.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(17), P. 10192 - 10280
Published: Aug. 8, 2024
Radical
C–H
functionalization
represents
a
useful
means
of
streamlining
synthetic
routes
by
avoiding
substrate
preactivation
and
allowing
access
to
target
molecules
in
fewer
steps.
The
first-row
transition
metals
(Ti,
V,
Cr,
Mn,
Fe,
Co,
Ni,
Cu)
are
Earth-abundant
can
be
employed
regulate
radical
functionalization.
use
such
is
desirable
because
the
diverse
interaction
modes
between
metal
complexes
species
including
addition
center,
ligand
complexes,
substitution
single-electron
transfer
radicals
hydrogen
atom
noncovalent
complexes.
Such
interactions
could
improve
reactivity,
diversity,
selectivity
transformations
allow
for
more
challenging
reactions.
This
review
examines
achievements
this
promising
area
over
past
decade,
with
focus
on
state-of-the-art
while
also
discussing
existing
limitations
enormous
potential
high-value
regulated
these
metals.
aim
provide
reader
detailed
account
strategies
mechanisms
associated
