Hexafluoroisopropanol (HFIP)-Promoted Hydrodifluoroalkylation of Furans and Vinyl Ethers Using Difluorinated Silyl Enol Ethers for the Synthesis of gem-Difluorinated Ethers
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 18, 2025
A
hexafluoroisopropanol
(HFIP)-promoted
hydrodifluoroalkylation
of
furans
and
vinyl
ethers
with
difluorinated
silyl
enol
has
been
developed.
Because
the
inherent
electron
richer
nature
poor
nucleophilicity
ethers,
employment
simple
as
substrates
for
nucleophilic
dearomatization
without
a
metal
or
stoichiometric
chemical
oxidizing
reagent
is
challenging,
especially
considering
rearomatization
driving
force
ring
fragmentation
furan
system.
This
protocol
exploits
formation
oxocarbenium
intermediate
from
using
HFIP
proton
source
to
allow
addition
which
provides
an
efficient
synthetic
strategy
install
gem-difluorinated
group
into
heterocycles.
Язык: Английский
(3+2) Annulation of Donor–Acceptor Cyclopropanes with Difluoroenoxysilanes: Syntheses of gem-Difluorocyclopentenes via α,α-Difluoroketone Scaffolds
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 27, 2025
Herein,
we
present
an
acid-
and
base-mediated
approach
for
ring
opening
of
donor-acceptor
cyclopropanes
(DACs)
followed
by
(3+2)
annulation,
yielding
biologically
relevant
gem-difluorinated
cyclopentenes
via
α,α-difluoroketone
scaffolds.
Fluorinated
rings
are
essential
building
blocks
in
drug
discovery
materials
research.
This
methodology
has
a
broad
substrate
scope,
is
scalable,
provides
practical
synthetic
route
to
obtain
value-added
fluorinated
compounds.
Язык: Английский
Synthesis of 2,3-Diperfluoroalkylated Quinoxalines via Selenium-Catalyzed Reductive C–C Coupling of Vicinal Perfluoroalkyl Formimidoyl Chlorides
Organic Letters,
Год журнала:
2024,
Номер
26(41), С. 8866 - 8871
Опубликована: Окт. 9, 2024
A
direct
and
efficient
approach
to
access
structurally
interesting
2,3-diperfluoroalkylated
quinoxalines
via
selenium-catalyzed
reductive
C-C
construction
of
vicinal
bis(perfluoroalkyl
formimidoyl
chloride)s
has
been
disclosed.
This
protocol
features
the
use
easily
accessible
starting
materials,
scalability,
a
diverse
functional
group
tolerance.
Mechanism
studies
suggested
that
this
reaction
may
involve
an
selenium-containing
seven-membered-ring
intermediate
proceed
through
electrocyclization/selenium
elimination
pathway,
which
is
significantly
different
from
traditional
transition-metal-catalyzed
coupling
strategies
alkyl
halides.
Язык: Английский