Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(70)
Published: Sept. 21, 2024
Abstract
The
synthesis
of
α‐tertiary
amino
acids
(ATAAs),
which
are
pivotal
components
in
natural
metabolism
and
pharmaceutical
innovation,
continues
to
attract
significant
research
interest.
Despite
substantial
advancements,
the
pursuit
a
facile,
versatile,
resource‐efficient
methodology
remains
an
area
active
development.
In
this
work,
we
introduce
visible
light‐triggered
three‐component
reaction
involving
readily
available
nitrosoarenes,
N
‐acyl
pyrazoles,
allyl
or
(bromomethyl)benzenes
under
mild
conditions.
This
approach
enables
straightforward
assembly
wide
array
ATAA
derivatives
(42
examples)
commendably
high
yields
(up
89
%).
Mechanistic
investigations
elucidate
that
proceeds
through
dehydration
condensation
between
nitrosoarenes
pyrazoles
generate
ketimine
intermediates.
is
followed
by
light‐driven
halogen
atom
transfer
(XAT)
process
radical
addition,
culminating
formation
desired
products.
showcases
excellent
functional
group
compatibility
late‐stage
derivatization
potential,
offering
new
insights
avenues
for
analogs.
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.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(50), P. 6340 - 6361
Published: Jan. 1, 2024
In
this
review,
the
state-of-the-art
advances
in
radical-involved
C(sp
3
)–N
bond
formation
via
metallaphotoredox
catalysis
have
been
highlighted,
which
are
organized
according
to
different
catalytic
modes,
reaction
types,
and
substrate
classes.
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.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(24), P. 15652 - 15662
Published: Nov. 21, 2023
Unveiling
the
alkyl/Pd
hybrid
species
is
a
unique
sp3-C-centered
radical
for
facilitating
intermolecular
hydrogen
atom
transfer
(HAT)
in
development
of
direct
alkylation
glycine
derivatives.
This
transformative
reaction
proceeds
smoothly
under
simple
and
mild
conditions,
exhibiting
impressive
versatility
terms
substrate
scope
encompassing
both
derivatives
alkyl
bromides
while
showcasing
remarkable
tolerance
toward
diverse
functional
groups.
To
shed
light
on
underlying
mechanism,
extensive
investigations
involving
control
experiments,
deuterium
labeling,
clocking,
kinetic
studies
have
been
conducted.
The
collected
data
consistently
support
pathway
formation
Pd(I)/alkyl
followed
by
HAT
elimination
steps
that
lead
to
situ
imine
intermediates,
ultimately
culminating
final
stage
through
addition.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Oct. 19, 2023
Photocatalytic
selective
C(sp3)-H
activation/cross-coupling
reactions
are
appealing
in
organic
synthesis.
In
this
manuscript,
we
describe
the
development
of
photoexcited-state
Pd-catalyzed
dehydrogenative
β-sulfonylation
using
amines
and
aryl
sulfonyl
chlorides
via
intermolecular
hydrogen
atom
transfer
C-S
cross-coupling
processes
at
room
temperature.
The
transformation
can
be
achieved
by
direct
generation
two
distinct
Pd-radical
hybrid
species
their
capability
to
promote
different
reactivities
from
Pd(0)
chlorides,
allowing
for
efficient
conversion
readily
available
into
stable
sulfonyl-substituted
enamines
in-depth
experimental,
computational,
transient
optical
spectroscopic
study
catalytic
applications
a
functionalization
event
provide
evidence
both
static
dynamic
quenching,
as
well
inner-sphere
outer-sphere
mechanisms.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(2), P. 1260 - 1269
Published: Jan. 6, 2023
The
reaction
of
organozinc
reagents
with
unactivated
imines
is
accelerated
when
performed
in
the
presence
a
photocatalyst
under
blue
light
irradiation.
Coordination
between
Lewis
acidic
zinc
iodide
and
imine
key
factor
responsible
for
efficiency.
method
can
be
carried
out
using
alkyl
iodides
Barbier
conditions.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(13), P. 2662 - 2667
Published: March 26, 2024
A
novel
class
of
alkyne-tethered
amides
facilitates
an
unprecedented
photoinduced
palladium-catalyzed
radical
relay
formal
[5
+
2]
reaction.
This
innovative
strategy
allows
for
the
rapid
construction
diverse
fused
benzoazepine
structures,
yielding
structurally
and
compelling
compounds.
With
a
broad
substrate
scope
excellent
functional
group
tolerance,
methodology
synthesizes
biologically
active
Notably,
resulting
tricyclic
benzo[b]azepines
offer
diversification
opportunities
through
simple
transformations.
DFT
calculations
elucidate
seven-membered
ring
closure
mechanism
involving
alkenyl
Pd(I)
rebound
alongside
concerted
metalation–deprotonation
(CMD)
process.
