Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(44), P. 9503 - 9507
Published: Oct. 28, 2024
Herein,
we
describe
a
dual
catalytic
strategy
that
employs
dihydroquinazolinones,
derived
from
ketone
analogs,
as
versatile
intermediates
for
acylation
via
α
C–C
cleavage
with
2-pyridyl
esters,
facilitating
the
efficient
synthesis
of
variety
ketones.
The
reaction
accommodates
wide
range
ketones
and
carboxylic
acids,
showing
tolerance
to
various
functional
groups.
versatility
this
synthetic
technique
is
further
highlighted
through
its
application
in
late-stage
modification
pharmaceuticals
biologically
active
natural
products.
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
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.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(15)
Published: March 15, 2024
Abstract
Low‐valent
chromium
catalysts
are
cheap
and
less
toxic
compared
to
other
transition
metal
catalysts.
Here
in,
we
reported
a
ligand‐free
chromium(III)‐catalyzed
manganese
reductive
cross‐coupling
of
unactivated
alkyl
electrophiles,
such
as
sulfonates
chlorides,
with
trisulfide
dioxides
thiolation
agents
form
carbon−sulfur
bonds.
The
powerful
method
featured
ample
substrate
scope
wide
functional
group
tolerance,
constructing
large
number
unsymmetrical
disulfides
under
simple
conditions.
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
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.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 10, 2025
Herein,
we
report
a
formal
C–C
bond
azidation
and
cyanation
of
unactivated
aliphatic
ketones
using
commercially
available
tosyl
azide
cyanide,
respectively.
A
visible-light-mediated
organophotocatalyst
enables
radical
ketone-derived
pro-aromatic
dihydroquinazolinones
(under
mostly
redox-neutral
conditions)
as
supported
by
preliminary
mechanistic
studies.
These
metal-free
scalable
protocols
can
be
used
to
synthesize
tertiary,
secondary,
primary
alkyl
azides
nitriles
with
good
functional
group
tolerance
postsynthetic
diversification
the
group,
including
bioconjugation.
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.
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.
