Multicomponent Synthesis of Alkyl BCP-Heteroaryls via Electron Donor–Acceptor Complex Photoactivation under Mild Conditions
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
90(4), С. 1683 - 1696
Опубликована: Янв. 17, 2025
In
the
vanguard
of
sustainable
chemistry,
pursuit
efficient
pathways
for
synthesis
alkyl
bicyclo[1.1.1]pentane-heteroaryls
has
captured
attention
scientific
vanguard.
We
herein
report
a
groundbreaking
and
eco-conscious
multicomponent
coupling
reaction
that
paves
way
alkylation
heteroarylation
[1.1.1]propellane,
process
uniquely
enabled
by
photochemical
prowess
an
electron
donor–acceptor
(EDA)
complex.
This
method
is
distinguished
its
minimalist
yet
powerful
approach:
devoid
transition
metals,
additives,
photosensitizers.
Its
universality
further
exemplified
seamless
compatibility
broad
spectrum
halides
heteroarenes
under
standardized
conditions,
heralding
new
era
synthetic
versatility.
The
method's
practicality
underscored
capacity
late-stage
modification
pharmaceuticals,
offering
transformative
tool
enhancement
existing
drug
molecules.
Moreover,
facile
derivatization
synthesized
products
underscores
adaptability
potential
diverse
applications.
Our
mechanistic
studies
have
elucidated
underlying
radical-relay
pathway,
pinpointing
pivotal
role
EDA
complex
in
initiating
transformation.
discovery
not
only
enriches
our
fundamental
understanding
but
also
opens
avenues
strategic
optimization.
Язык: Английский
Visible-Light-Induced Divergent C–H Esterification/Alkylation of Quinoxalin-2(1H)-ones with Aldehydes under Mild Conditions
Organic Letters,
Год журнала:
2025,
Номер
27(10), С. 2526 - 2531
Опубликована: Март 5, 2025
Herein,
we
introduce
an
efficient
and
straightforward
strategy
for
the
selective
C-H
esterification
alkylation
of
quinoxalin-2(1H)-ones
with
aldehydes.
A
key
feature
our
study
is
ability
to
perform
both
using
different
types
The
reaction
system
highly
compatible
a
range
aldehydes,
yielding
C3-esterified
C3-alkylated
products
in
moderate-to-good
yields.
applicability
this
approach
further
enhanced
by
its
scalability
through
continuous-flow
synthesis,
late-stage
modification
significant
molecules,
product
derivatization.
Our
mechanistic
investigations
reveal
radical
relay
mechanism,
triggered
hydrogen
atom
transfer
process.
Язык: Английский
A Mechanistic Perspective on Photocatalytic EnT-Enabled C3-N-Heteroarylation of Aryl Quinoxaline via C(sp2)–C(sp2) Coupling
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 11, 2025
An
EnT-mediated
C3-N-heteroarylation
of
2-aryl
quinoxalines
via
decarboxylative
radical-radical
cross-coupling
(C(sp2)-C(sp2))
with
oxime
esters
is
presented.
Upon
photoactivation,
the
triplet
energy
photocatalyst
transferred
to
both
reacting
partners
(oxime
ester
and
2-phenylquinoxaline).
The
excited
undergoes
fragmentation
a
C-centered
N-heteroaryl
radical
an
N-centered
imine
radical.
former
attacks
C3
site
quinoxaline
diradical,
while
latter
acts
as
hydrogen
atom
abstractor
(HAA).
Computational
studies
revealed
that
C-C
bond
formation
heteroaryl
energetically
more
favorable
than
C-N
formation.
Язык: Английский