Photochemical Dual Radical Coupling of Carboxylates with Alkenes/Heteroarenes via Diradical Equivalents
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 24, 2025
Carboxylate
diradical
intermediates,
with
α-carbon
and
carboxylic
oxygen
acting
as
reactive
radical
centers,
represent
a
highly
attractive
long-sought
species
in
reaction
design
synthesis.
However,
capturing
these
intermediates
for
coupling
reactions
poses
formidable
challenge
due
to
their
inherent
instability
spontaneous
decarboxylation.
Here,
we
addressed
this
by
temporarily
masking
the
carboxylate
reactivity
via
photocleavable
dynamic
oxygen–iodine
bond.
This
approach
effectively
prevents
unwanted
decarboxylation
enables
controlled
utilization
of
forming
new
bonds.
Carboxylates
alkenes/heteroarenes,
among
most
readily
available
raw
materials,
can
now
seamlessly
couple
pathways
form
γ-butyrolactones,
which
are
common
motifs
found
numerous
natural
products
bioactive
molecules.
Ionic
traditional
carboxylates
ruled
out
based
on
experimental
studies
density
functional
theory
(DFT)
calculations.
strategy
overcomes
substrate
limitations
methods,
significantly
expanding
range
applicable
alkenes/heteroarenes.
Our
method
allows
transforming
alkenes
modes
diverse
offers
insights
into
developing
di-
multiradical
equivalents
unprecedented
synthetic
designs.
Язык: Английский
Collective Synthesis of Furanocoumarin Natural Products through a Radical‐mediated Construction of Furanocoumarin Skeletons
Asian Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 13, 2024
Abstract
Furanocoumarins
are
attractive
targets
in
the
synthetic
organic
and
medicinal
chemistry
field
because
of
their
structural
diversity
interesting
biological
properties.
Herein,
we
describe
synthesis
furanocoumarin
natural
products
from
common
skeletons.
A
key
step
was
a
novel
intramolecular
radical
cyclization
onto
nitrile
to
synthesize
angular
linear
franocoumarins,
which
optimized
by
reacting
iodocoumarin
derivatives
presence
(Me
3
Si)
SiH
oxygen.
These
compounds
served
as
intermediates
syntheses
vaginidiol,
vaginidin,
oroselol,
multivittan
D,
gaudichaudine,
oreoselone,
peucedanin,
smyrindiol,
successfully
demonstrating
versatility
utility
method
for
accessing
products.
Язык: Английский