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
Heterogeneous g-C3N4/NaI Dual Catalytic Difunctionalization of Alkenes with Heteroarenes and Methyl Carbazate under Visible Light
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 26, 2025
Herein,
a
photoinduced
heterogeneous
catalytic
system
merging
g-C3N4
and
NaI
has
been
established
for
the
difunctionalization
of
alkenes
in
conjunction
with
heteroarenes
methyl
carbazate.
This
approach
is
notable
its
broad
substrate
tolerance,
encompassing
wide
range
leading
to
formation
corresponding
esters
moderate
good
yields.
Additionally,
scalability
synthetic
process
versatility
product
transformations
have
illustrated,
highlighting
potential
practical
application
organic
synthesis.
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
Visible-Light-Mediated Perfluoroalkylation/Thioetherification of [1.1.1]Propellane under Photocatalyst-Free Conditions
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 29, 2025
Perfluoroalkyl-functionalized
bicyclo[1.1.1]pentane
(BCP)
derivatives
have
garnered
significant
attention
in
pharmaceuticals
due
to
their
special
physicochemical
property;
however,
establishing
convenient
synthetic
protocols
for
these
fluorinated
molecular
frameworks
continues
present
substantial
methodological
challenges.
Herein,
we
report
a
photocatalyst
and
additive-free
perfluoroalkylation/thioetherification
of
[1.1.1]
propellane
with
disulfide
ether
perfluoroalkyl
iodines.
Such
photochemistry
methodology
utilizing
an
electron
donor-acceptor
(EDA)
complex
offers
green
novel
way
obtain
various
BCP
containing
thioether
groups
good
functional
group
tolerance.
Язык: Английский