Asian Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
13(6)
Published: April 18, 2024
Abstract
Electron‐donor
acceptor
(EDA)
complex
has
been
an
integral
part
of
visible‐light
photocatalysis
and
is
different
from
the
traditional
photoredox
catalysis,
which
requires
exogenous
photocatalyst,
typically
a
colored
compound
to
initiate
photocatalytic
cycle.
Interestingly,
EDA‐complex
photochemistry
found
profound
use
in
activating
inert
α‐C−H
bonds
amines.
The
strategy
relied
upon
formation
between
donor
(amine)
(Lewis
acid),
harvesting
light
energy
perform
SET
process
generate
radical
cation
anion
intermediates.
then
loses
activated
acidic
proton
(because
SET,
acidity
α‐proton
increases
by
lowering
BDE)
form
α‐amino
radical,
participates
various
C−C
coupling
cascades.
In
this
review,
conceptual
approaches
for
generation
radicals
their
bond‐forming
reaction
under
triggered
will
be
discussed
with
particular
emphasis
on
mechanism
2018
onwards.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(49), P. 22451 - 22457
Published: Dec. 1, 2022
Amines
featuring
an
adjacent
stereocenter
are
important
building
blocks,
and
recent
years
have
seen
remarkable
growth
in
methods
forming
these
via
prochiral
α-amino
radical
intermediates.
However,
very
few
can
exert
control
over
the
newly
formed
stereocenter.
We
disclose
a
strategy
to
overcome
this
context
of
one
most
widely
used
carbon–carbon
bond
reactions,
Giese
reaction.
Incorporation
removable
basic
heteroarene
into
substrate
enables
network
attractive
noncovalent
interactions
between
phosphoric
acid
catalyst,
subsequently
radical,
acceptor,
allowing
catalyst
during
C–C
step.
Deprotection
products
leads
analogues
γ-aminobutyric
acid.
anticipate
that
will
be
applicable
other
asymmetric
transformations
which
is
presently
challenging.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(45)
Published: Sept. 18, 2023
The
catalytic
C(sp3
)-C(sp3
)
coupling
of
alkyl
halides
and
tertiary
amines
offers
a
promising
tool
for
the
rapid
decoration
amine
skeletons.
However,
this
approach
has
not
been
well
established,
partially
due
to
challenges
in
precisely
distinguishing
controlling
reactivity
amine-coupling
partners
their
product
homologues.
Herein,
we
developed
metal-free
photocatalytic
system
aminomethylation
through
radical-involved
bond
formation,
allowing
synthesis
sterically
congested
that
are
interest
organic
but
easily
prepared
by
other
methods.
Mechanistic
studies
disclosed
hindered
N-substituents
key
activate
tuning
redox
potentials
drive
reaction
forward.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(2)
Published: Nov. 6, 2023
Abstract
Thiolate‐protected
gold
nanoclusters
(AuNCs)
have
attracted
significant
attention
as
nano‐catalysts,
revealing
a
superatomic
core
and
gold‐thiolate
staples
distinct
structural
units.
Here,
we
demonstrate
the
unprecedented
dual
catalytic
activity
of
thiolate‐protected
[Au
25
(SR)
18
]
−
nanoclusters,
involving
both
photosensitized
1
O
2
generation
by
Au
13
carbon‐carbon
bond
formation
facilitated
3
staples.
This
synergistic
combination
two
different
units
enables
efficient
cross‐dehydrogenative
coupling
terminal
alkynes
tertiary
aliphatic
amines
to
afford
propargylamines
in
high
yields
up
93
%.
Mixed‐ligand
AuNCs
bearing
thiolate
alkynyl
ligands
revealed
intermediacy
alkynyl‐exchanged
toward
photosensitization
C−C
bond‐forming
cycles.
Density
functional
theory
calculations
also
supported
AuNCs.
Thus,
use
ligand‐protected
metal
has
enabled
development
an
exceptional
multifunctional
catalyst,
wherein
nanocluster
components
facilitate
cooperative
photo‐
chemo‐catalysis.
Asian Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
13(6)
Published: April 18, 2024
Abstract
Electron‐donor
acceptor
(EDA)
complex
has
been
an
integral
part
of
visible‐light
photocatalysis
and
is
different
from
the
traditional
photoredox
catalysis,
which
requires
exogenous
photocatalyst,
typically
a
colored
compound
to
initiate
photocatalytic
cycle.
Interestingly,
EDA‐complex
photochemistry
found
profound
use
in
activating
inert
α‐C−H
bonds
amines.
The
strategy
relied
upon
formation
between
donor
(amine)
(Lewis
acid),
harvesting
light
energy
perform
SET
process
generate
radical
cation
anion
intermediates.
then
loses
activated
acidic
proton
(because
SET,
acidity
α‐proton
increases
by
lowering
BDE)
form
α‐amino
radical,
participates
various
C−C
coupling
cascades.
In
this
review,
conceptual
approaches
for
generation
radicals
their
bond‐forming
reaction
under
triggered
will
be
discussed
with
particular
emphasis
on
mechanism
2018
onwards.
