Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(50)
Опубликована: Июнь 2, 2023
Alkyl
radical
precursors
are
essential
for
a
wide
variety
of
photocatalytic
and
3d-metal-catalyzed
C-C
bond
forming
reactions.
Neutral
organic
heterocycles
as
electroauxiliaries
such
4-alkyl
Hantzsch
esters
have
become
reliable
tools
alkyl
formation.
Here
we
show
that
2,2'-biquinoline-derived
alkyl-substituted
dihydroquinolines
act
competent
with
the
ability
to
form
primary,
secondary
tertiary
radicals.
Hydroalkylation
benzalmalononitriles
N-Boc
protected
diazenes
has
been
achieved
through
copper
catalysis
under
mild
conditions
50
°C
good
very
yields
up
85
%.
Furthermore,
dihydroquinolines'
reactivity
towards
denitrative
alkylation
nitroolefins
β-nitrostyrene
was
discovered.
Most
importantly,
released
biquinoline
can
be
recycled,
which
greatly
improves
overall
atom-economy
these
in
comparison
previous
N-heterocyclic
electroauxiliaries.
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.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(32), С. 22829 - 22839
Опубликована: Авг. 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
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(8)
Опубликована: Дек. 28, 2022
Herein,
we
describe
the
development
of
a
copper-catalyzed
C(sp3
)-amination
proaromatic
dihydroquinazolinones
derived
from
ketones.
The
reaction
is
enabled
by
intermediacy
open-shell
species
arising
homolytic
C-C
bond-cleavage
driven
aromatization.
protocol
characterized
its
operational
simplicity
and
generality,
including
chemical
diversification
advanced
intermediates.
Organic Letters,
Год журнала:
2023,
Номер
25(9), С. 1441 - 1446
Опубликована: Фев. 23, 2023
A
visible-light-photocatalyzed
1,2-arylalkylation
of
N-(arylsulfonyl)acrylamides
with
ketone-based
dihydroquinazolinones
is
described.
The
formal
C-C
bond
cleavage
aliphatic
ketones
unified
tandem
radical
alkylation/1,4-aryl
migration/desulfonylation
to
forge
two
different
types
vicinal
bonds
and
construct
an
all-carbon
quaternary
α-stereocenter,
thus
enhancing
the
carbogenic
complexity
tolerating
diverse
functionalities.
Additional
telescopic
synthesis
product
diversification,
this
method
features
a
dicarbofunctionalization
conjugated
nucleophilic
alkyl
precursor
(dihydroquinazolinone)
utilizing
oxygen
as
green
oxidant
at
ambient
temperature.
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,
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.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(38), С. 21096 - 21103
Опубликована: Сен. 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.
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.
