Chemical Communications,
Год журнала:
2023,
Номер
59(91), С. 13643 - 13646
Опубликована: Янв. 1, 2023
An
aminoquinolate
diarylboron
(AQDAB)
and
tetrabutylammonium
iodide
(TBAI)
co-catalyzed
photoredox
process
for
N-functionalization
of
NH-sulfoximines/sulfonimidamides
has
been
successfully
developed.
This
protocol
can
afford
the
corresponding
N-sulfenylated
N-phosphonylated
products
in
good
to
excellent
yields
under
conditions
without
metallic
(photo)catalysts,
external
oxidants,
or
acidic/basic
additives.
A
wide
range
functional
groups
are
tolerated,
NH-sulfonimidamides
have
reported
first
time.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(8)
Опубликована: Янв. 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
Chemical Science,
Год журнала:
2024,
Номер
15(23), С. 8993 - 8999
Опубликована: Янв. 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.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 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.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(22)
Опубликована: Апрель 16, 2024
Abstract
In
this
study,
we
present
an
efficient
and
straightforward
dearomative
hydroalkylation
of
indoles.
By
utilizing
alkanes
or
ethers
as
alkyl
radical
sources
employing
TBADT
a
cost‐effective
photocatalyst
for
direct
hydrogen
atom
transfers
(HAT),
achieved
successful
conversion
these
heterocyclic
derivatives
into
2‐alkylindolines
with
good
to
excellent
yields
high
diastereoselectivity
under
mild
reaction
conditions.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 7, 2025
The
homolytic
cleavage
of
C–C
bonds
adjacent
to
specific
functional
groups
has
lately
emerged
as
a
versatile
approach
for
molecular
diversification.
Despite
the
ubiquity
and
synthetic
utility
ketones,
radical
fragmentation
their
α-C–C
proven
be
formidable
challenge.
Here,
we
present
broadly
applicable
deacylative
strategy
designed
homolytically
cleave
aliphatic
ketones
various
complexities,
including
transformations
cycloalkanones
into
carboxylic
acids
tethered
C-centered
free
radicals
that
can
engaged
in
diverse
radical-based
processes.
method
involves
ketone
activation
through
treatment
with
hydrogen
peroxide,
yielding
gem-dihydroperoxides.
Subsequent
single-electron-transfer
reduction
mediated
by
low-valent
metal
complex
generates
alkyl
captured
selectively
radicophile
choice,
catalytic
cross-coupling.
logic
our
functionalization
is
exemplified
total
synthesis
14
natural
products,
one
analogue,
two
drugs
starting
from
readily
available
showcasing
its
transformative
power
settings.
This
obviates
need
reagents
allows
controlled
conversion
reconstructed
making
process
highly
across
spectrum
domains.
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,
Год журнала:
2023,
Номер
88(16), С. 12121 - 12130
Опубликована: Июль 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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 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 & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(27), С. 5561 - 5568
Опубликована: Янв. 1, 2024
An
organo-photoredox
catalyzed
defluorinative
alkylation
of
ketone-derived
dihydroquinazolinones
with
α-trifluoromethyl
alkenes
is
described,
providing
a
facile
access
to
diverse
set
gem
-difluoroalkenes.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(58)
Опубликована: Авг. 8, 2024
Abstract
Mild
and
inexpensive
copper‐catalyzed
aromatization‐driven
ring‐opening
amination
oxygenation
of
spiro
dihydroquinazolinones
are
presented,
respectively.
These
protocols
provide
facile
atom‐economical
access
to
the
aminated
carbonyl‐containing
quinazolin‐4(3
H
)‐ones
in
good
yields
with
functional
group
compatibility,
which
difficult
obtain
by
conventional
methods.
Remarkably,
a
telescoped
procedure
involving
condensation
ring‐opening/functionalization
for
simple
cycloalkanone
was
found
be
accessible.
Mechanistic
studies
suggest
radical
pathway
this
transformation.
