Science Advances,
Journal Year:
2024,
Volume and Issue:
10(17)
Published: April 26, 2024
Ketones
are
ubiquitous
in
bioactive
natural
products,
pharmaceuticals,
chemical
feedstocks,
and
synthetic
intermediates.
Hence,
deacylative
coupling
reactions
enable
the
versatile
elaboration
of
a
plethora
chemicals
to
access
complex
drug
candidates
products.
Here,
we
present
arylation
alkynylation
strategies
for
synthesis
wide
range
alkyl-tethered
arenes
alkynes
from
cyclic
ketones
methyl
under
dual
nickel/photoredox
catalysis.
This
reaction
begins
by
generating
pre-aromatic
intermediate
(PAI)
through
condensation
ketone
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(25), P. 3655 - 3664
Published: Jan. 1, 2023
This
highlight
summarises
electrochemical
approaches
for
the
generation
and
utilization
of
alkoxy
radicals,
predominantly
focusing
on
recent
advances
(2012–present).
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(23), P. 8993 - 8999
Published: Jan. 1, 2024
The
aromatization-driven
deconstructive
coupling
of
spiro
carbocycles
with
organic
halides
via
dual
photoredox/nickel
catalysis
is
developed.
An
in-depth
mechanism
study
revealed
that
this
reaction
proceeded
a
radical-metal
crossover
pathway.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 18, 2024
ConspectusChemists
have
long
pursued
harnessing
light
energy
and
photoexcitation
processes
for
synthetic
transformations.
Ligand-to-metal
charge
transfer
(LMCT)
in
high-valent
metal
complexes
often
triggers
bond
homolysis,
generating
oxidized
ligand-centered
radicals
reduced
centers.
While
photoinduced
oxidative
activations
can
be
enabled,
this
process,
typically
seen
as
photochemical
decomposition,
remains
underexplored
catalytic
applications.
To
mitigate
decomposition
during
LMCT
excitation,
we
developed
a
cycle
integrating
situ
coordination,
LMCT,
ligand
homolysis
to
activate
ligated
alcohols
transiently
into
alkoxy
radicals.
This
approach
leverages
Ce(IV)
excitation
highly
reactive
radical
intermediates
selective
functionalizations
of
C(sp
Science Advances,
Journal Year:
2024,
Volume and Issue:
10(17)
Published: April 26, 2024
Ketones
are
ubiquitous
in
bioactive
natural
products,
pharmaceuticals,
chemical
feedstocks,
and
synthetic
intermediates.
Hence,
deacylative
coupling
reactions
enable
the
versatile
elaboration
of
a
plethora
chemicals
to
access
complex
drug
candidates
products.
Here,
we
present
arylation
alkynylation
strategies
for
synthesis
wide
range
alkyl-tethered
arenes
alkynes
from
cyclic
ketones
methyl
under
dual
nickel/photoredox
catalysis.
This
reaction
begins
by
generating
pre-aromatic
intermediate
(PAI)
through
condensation
ketone