Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(34)
Published: June 28, 2023
Abstract
Activation
of
C−C
bonds
allows
editing
molecular
skeletons,
but
methods
for
selective
activation
nonpolar
in
the
absence
a
chelation
effect
or
driving
force
derived
from
opening
strained
ring
are
scarce.
Herein,
we
report
method
ruthenium‐catalyzed
pro‐aromatic
compounds
by
means
π‐coordination‐enabled
aromatization.
This
was
effective
cleavage
C−C(alkyl)
and
C−C(aryl)
ring‐opening
spirocyclic
compounds,
providing
an
array
benzene‐ring‐containing
products.
The
isolation
methyl
ruthenium
complex
intermediate
supports
mechanism
involving
ruthenium‐mediated
bond
cleavage.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(8)
Published: Jan. 8, 2024
A
mild
photoredox
catalyzed
construction
of
sulfides,
disulfides,
selenides,
sulfoxides
and
sulfones
from
unstrained
ketone
precursors
is
introduced.
Combination
this
deacylative
process
with
S
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(32), P. 22829 - 22839
Published: Aug. 1, 2024
The
molecular
editing
of
ketones
represents
an
appealing
strategy
due
to
its
ability
maximize
the
structural
diversity
ketone
compounds
in
a
straightforward
manner.
However,
developing
efficient
methods
for
arbitrary
modification
ketonic
molecules,
particularly
those
integrated
within
complex
skeletons,
remains
significant
challenge.
Herein,
we
present
unique
recasting
that
involves
radical
acylation
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
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(32), P. 6915 - 6920
Published: Aug. 8, 2024
Ketones,
as
essential
functional
group
skeletons,
have
garnered
significant
interest
due
to
their
diverse
transformations.
Herein,
we
describe
a
versatile
photoredox
catalyzed
deacylation-aroylation
strategy
that
enables
the
direct
transformation
of
alkyl
ketones
aryl
ketones.
This
process
involves
deacylation
dihydroquinazolinones
derived
from
generate
radicals,
followed
by
subsequent
NHC-catalyzed
or
NHC-mediated
radical
aroylation.
Chemical Communications,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
We
report
an
organophotocatalyst-enabled
oxidant-free
C–S/C–Se
bond
coupling
of
(un)symmetrical
1,2-diketones
via
pro-aromatic
dihydroquinazolinones/benzothiazolines,
employing
readily
accessible
disulfides/diselenides.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(16), P. 12121 - 12130
Published: July 29, 2023
We
describe
a
visible-light
photoredox-catalyzed
alkylation/arylative
cyclization
of
N-acrylamides─from
2-arylindoles,
2-arylbenzimidazoles,
or
N-substituted
anilines─with
ketone-derived
dihydroquinazolinones,
accessing
indolo-
and
benzimidazolo[2,1-a]isoquinolines
2-oxindoles.
The
consecutive
incorporation
alkyl-
aryl-carbogenic
motifs
across
C=C
bond
via
formal
cleavage
ketone
α-C-C
arene
C-H
bonds
leads
to
the
formation
five-
six-membered
rings,
with
an
all-carbon
quaternary
stereocenter.
This
dicarbofunctionalization
elaborates
aromatization-driven
radical
C-C
functionalization
unactivated
aliphatic
ketones
construct
diverse
cyclic
structures
functionality
tolerance.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(38), P. 21096 - 21103
Published: Sept. 15, 2023
Alkyl
halides
are
versatile
precursors
to
access
diverse
functional
groups
(FGs).
Due
their
lability,
the
development
of
surrogates
for
alkyl
is
strategically
important
complex
molecule
synthesis.
Given
stability
and
ease
derivatization
inherent
in
common
ketones,
here
we
report
a
deacylative
halogenation
approach
convert
various
methyl
ketones
corresponding
chlorides,
bromides,
iodides.
The
reaction
driven
by
forming
an
aromatic
byproduct,
i.e.,
1,2,4-triazole,
which
N′-methylpicolinohydrazonamide
(MPHA)
employed
form
prearomatic
intermediate
halogen
atom-transfer
(XAT)
reagents
used
quench
radical
intermediate.
efficient
yielding
primary
secondary
from
wide
range
with
broad
FG
tolerance.
It
also
works
natural-product-derived
fluoro-containing
substrates.
In
addition,
one-pot
conversions
other
FGs
annulations
alkenes
alkynes
through
realized.
Moreover,
unusual
iterative
homologation
iodides
demonstrated.
Finally,
mechanistic
studies
reveal
intriguing
double
XAT
process
iodination
reaction,
could
have
implications
beyond
this
work.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 24, 2024
Abstract
The
homolysis
of
chemical
bonds
represents
one
the
most
fundamental
reactivities
excited
molecules.
Historically,
it
has
been
exploited
to
generate
radicals
under
ultraviolet
(UV)
light
irradiation.
However,
unlike
contemporary
radical‐generating
mechanisms,
direct
excitation
homolyze
and
produce
aliphatic
carbon‐centered
visible
remains
rare,
especially
in
metallaphotoredox
cross
couplings.
Herein,
we
present
our
design
dihydropyrimidoquinolinone
(DHPQ)
reagents
derived
from
ketones,
which
can
undergo
formal
deacylation
homolytic
C−C
bond
cleavage
release
alkyl
without
external
photocatalysts.
Spectroscopic
computational
analysis
reveal
unique
optical
structural
features
DHPQs,
rationalizing
their
faster
kinetics
radical
generation
than
a
structurally
similar
but
visible‐light
transparent
precursor.
Such
capability
allows
DHPQ
facilitate
wide
range
Ni‐metallaphotoredox
couplings
with
aryl,
alkynyl
acyl
halides.
Other
catalytic
non‐catalyzed
alkylative
transformations
DHPQs
are
also
feasible
various
acceptors.
We
believe
this
work
would
be
broad
interest,
aiding
synthetic
planning
simplified
operation
expanding
reach
photocatalyst‐free
approaches
cutting‐edge
research.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Aug. 25, 2024
Due
to
the
high
reactivity
and
versatility
of
benzenesulfonothioates,
significant
advancements
have
been
made
in
constructing
C-S
bonds.
However,
there
are
certain
limitations
synthesis
S-thiosulfonates
SS-thiosulfonates,
especially
when
dealing
with
substantial
steric
hindrance,
which
poses
a
challenge.
Herein,
we
present
an
innovative
approach
for
assembling
unsymmetric
SS-thiosulfonates
through
integration
dual
copper/photoredox
catalysis.
Moreover,
also
realized
one-pot
strategy
by
directly
using
carboxylic
acids
as
raw
materials
in-situ
activation
them
access
without
further
purification
presynthesis
NHPI
esters.
The
envisaged
utilization
these
reagents
poised
pioneer
pathway
fabricating
versatile
spectrum
mono-,
di-,
polysulfide
compounds.
Furthermore,
they
introduce
class
potent
sulfenylating
reagents,
empowering
intricate
unsymmetrical
disulfides
that
were
previously
challenging
access.
conventional
method
synthesizing
thioether
compounds
typically
relies
on
thiol,
disulfide,
sulfinyl
halide
initial
substances,
suffering
from
strong
odors,
limited
availability,
issues.
Here,
authors
catalysis
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 13, 2025
A
class
of
prearomatic
carboxylic
acid
p-quinol
ester
radical
precursors
has
been
developed
successfully,
which
could
undergo
homolytic
cleavage
the
para
C-O
bond
esters
via
pyridine-boryl
radical-induced
aromatization
in
presence
pyridines
and
diboron
reagents,
affording
corresponding
alkyl
decarboxylation
from
carboxyl
situ.
In
addition,
were
further
applied
substitution
with
phenylsulfonyl
compounds
self-coulpings.
This
method
not
only
provides
a
new
approach
to
generation
intermediate
but
also
expands
application
boron
radicals.
