Dearomative 1,4-Difunctionalization of Non-Activated Arenes Enabled by Boryl Radical-Mediated Halogen-Atom Transfer
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 1294 - 1304
Опубликована: Янв. 7, 2025
Given
the
widespread
presence
of
spirocyclic
scaffolds
in
natural
products
and
pharmacologically
relevant
synthetic
compounds,
development
efficient
methodologies
for
their
construction
holds
great
importance
medicinal
chemistry
pharmaceutical
research.
In
this
study,
a
general
photochemical
dearomative
spirocyclization
nonactivated
arenes
has
been
established.
The
key
to
method
lies
ability
amine-borane
radicals
activate
aryl
bromides
iodides
via
halogen-atom
transfer,
thereby
allowing
conversion
halides
into
corresponding
subsequent
chemodivergent
transformations.
remarkable
compatibility
versatility
1,4-difunctionalization
is
showed
by
rapid
assembly
structurally
diverse
1,4-cyclohexadiene-based
spirocycles
incorporating
oxindole,
indoline,
or
dihydrobenzofuran
subunits.
Moreover,
potential
utility
protocol
exemplified
formal
total
synthesis
vasopressin
V2
receptor
antagonist
Satavaptan.
Язык: Английский
Expedient Cyano‐hydroxylation of Alkenes Enabled by Halogen Atom Transfer Induced Radical Ring‐Opening Elaboration of 3‐Bromo‐isoxazoline Cycloadducts
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 19, 2025
Comprehensive
Summary
Herein,
we
present
a
highly
efficient
one‐pot,
two‐step
synthesis
of
β
‐hydroxy
nitrile
scaffolds,
which
possess
both
significant
synthetic
value
and
notable
biological
activity,
starting
from
readily
accessible
alkenes.
This
methodology
relies
crucially
on
the
seamless
integration
regioselective
(3+2)
cycloaddition
reaction,
employing
commercially
available
1,1‐dibromoformaldoxime
as
1,3‐dipole
precursor,
with
subsequent
halogen
atom
transfer‐induced
radical
ring‐opening
elaboration
resulting
3‐bromo‐2‐isoxazoline
cycloadducts.
protocol
is
featured
by
mild
reaction
conditions,
broad
alkene
scope
various
derivatizations
obtained
cyano‐hydroxylation
products,
offering
versatile
practical
pathway
to
accessing
multi‐functionalized
molecules.
Язык: Английский
Traceless Aminoalkyl Radical-Induced Halogen-Atom Transfer for Minisci Reactions
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Июнь 4, 2025
Halogen-atom
transfer
(XAT)
provides
a
viable
strategy
to
convert
alkyl
halides
into
the
corresponding
carbon
radicals,
but
usage
of
equivalent
XAT
reagents
and
excess
oxidants
is
usually
inevitable.
Herein,
we
present
traceless
aminoalkyl
radical-induced
process
for
Minisci
reaction,
especially
without
participation
under
redox-neutral
conditions.
Mechanistic
experiments
indicated
that
formation
comparable
radicals
occurred
through
single-electron
reduction
protonated
heteroaromatics,
differing
from
conventional
oxidation
amines
used
generate
α-aminoalkyl
radicals.
Язык: Английский
Visible-Light-Induced Photoredox Construction of Trifluoromethylated Quaternary All-Carbon Centers and Tertiary Alcohols via C(sp3)–Si Bond Cleavage
Synthesis,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 10, 2024
Abstract
The
construction
of
trifluoromethylated
quaternary
carbon
centers
and
tertiary
alcohols
is
realized
by
organo-photoredox
catalysis.
process
proceeds
via
visible-light-induced
C(sp3)–Si
bond
cleavage
for
the
generation
α-trifluoromethylated
benzyl
radicals,
which
are
readily
trapped
electron-deficient
alkenes
with
excellent
regioselectivity
all-carbon
centers.
α-difluoromethyl
counterparts
also
suitable
this
radical
conjugate
addition.
Furthermore,
in
situ
oxidation
these
radicals
O2
from
air
affords
high
yields,
extends
Fleming–Tamao
reaction
to
systems.
Язык: Английский