Molecules,
Год журнала:
2024,
Номер
29(3), С. 697 - 697
Опубликована: Фев. 2, 2024
A
novel,
efficient
and
environmentally
friendly
solvent-free
catalyst-free
approach
for
the
synthesis
of
structurally
diverse
gem-difluorinated
polyfluoroarylated
derivatives
with
readily
available
nucleophilic
electrophilic
fluorine-containing
reaction
partners,
difluoroenoxysilane
pentafluorobenzaldehyde,
is
described.
This
neat
protocol
induced
by
direct
hydrogen-bond
interactions
between
fluorinated
non-fluorinated
reactants
without
use
heavy
metal
catalysts
or
volatile
organic
solvents
no
need
column
chromatographic
separation
most
cases.
Organic Letters,
Год журнала:
2024,
Номер
26(3), С. 751 - 756
Опубликована: Янв. 12, 2024
A
highly
diastereoselective
[3
+
2]
cycloaddition
of
aziridines
with
difluorinated
silyl
enol
ethers
has
been
developed.
This
approach
provides
a
facile
methodology
for
functionalized
gem-difluorinated
pyrrolidines
in
good
to
excellent
yields
functional
group
tolerance.
one-pot,
two-step
synthesis
structurally
interesting
fluorinated
pyrroles
also
developed
through
cycloaddition/aromatization/desulfonation
sequence.
Moreover,
readily
available
substrates,
mild
reaction
conditions,
and
easy
scale-up
show
practical
advantages.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(5), С. 2847 - 2857
Опубликована: Фев. 16, 2024
In
recent
years,
the
application
of
fluorinated
alcohols
as
solvents,
cosolvents,
or
additives
has
become
important
in
modern
organic
synthesis.
However,
their
potential
efficient
catalysts
synthesis
not
been
well-explored.
this
article,
we
report
on
development
a
one-pot
sequential
cascade
reaction
p-quinone
methides
with
difluoroenoxysilanes
using
hexafluoroisopropanol
catalyst.
This
allows
for
preparation
multisubstituted
oxa-spiro[4,5]cyclohexadienones.
By
50
mol
%
1,1,1,3,3,3-Hexafluoroisopropanol
(HFIP),
proceeds
smoothly
to
yield
1,6-conjugated
products,
which
are
then
subjected
oxidative
dearomatization/hemiacetalization
PhI(OAc)2.
The
overall
process
affords
moderate
high
yields
and
excellent
diastereoselectivities.
Organic Letters,
Год журнала:
2023,
Номер
25(26), С. 4908 - 4912
Опубликована: Июнь 23, 2023
A
decarboxylative/dehydrofluorinative
formal
[3
+
2]
cycloaddition
aromatization
of
isoquinolinium
N-ylides
with
difluoroenoxysilanes
has
been
developed.
This
methodology
provides
a
facile
and
straightforward
synthetic
pathway
to
afford
highly
functionalized
fluorinated
pyrrolo[2,1-a]isoquinolines
in
good
excellent
yields
under
mild
conditions.
Moreover,
gram-scale
derivatization
experiments
for
the
late-stage
functionalization
drug
molecules
have
also
demonstrated.
Organic Letters,
Год журнала:
2024,
Номер
26(7), С. 1447 - 1451
Опубликована: Фев. 14, 2024
Difluoroenoxysilane,
a
commonly
used
difluoroallylating
reagent,
has
attracted
considerable
attention
in
recent
years.
However,
its
application
the
annulation
reaction
for
construction
of
fluorinated
heterocyclic
compounds
remains
relatively
limited.
Presented
here
is
Brønsted
acid-catalyzed
efficient
formal
[4
+
2]
difluoroenoxysilanes
with
α-cyano
chalcones.
The
developed
protocol
demonstrates
tolerance
to
various
substituents
under
mild
conditions,
providing
reliable
approach
construct
gem-difluoro-3,4-dihydro-2H-pyrans
good
excellent
yields
high
diastereoselectivities.
Asian Journal of Organic Chemistry,
Год журнала:
2024,
Номер
13(4)
Опубликована: Фев. 24, 2024
Abstract
A
catalyst‐free
intermolecular
dearomatization
reaction
of
β
‐naphthols
with
hypervalent‐iodine‐based
nitrooxylating
reagent
is
reported.
Various
nitrooxylated
‐naphthalenones
bearing
a
quaternary
carbon
stereogenic
center
were
obtained
smoothly
in
good
to
excellent
yields
(up
87
%)
under
mild
conditions.
This
method
features
conditions,
broad
substrate
scope
and
chemoselectivity.
Organic Letters,
Год журнала:
2024,
Номер
26(22), С. 4610 - 4615
Опубликована: Май 23, 2024
An
oxa-6π-electrocyclization
of
difluoroenoxysilanes
with
diaryl
2-indolylmethanols
has
been
developed.
In
addition,
a
rarely
reported
C3-nucleophilic
[3+2]
cycloaddition
dialkyl
disclosed.
This
divergent
approach
affording
readily
available
as
three-atom
and
C2
synthons
provides
rapid
access
to
fluoro
2
Organic Letters,
Год журнала:
2022,
Номер
24(30), С. 5557 - 5561
Опубликована: Июль 22, 2022
An
efficient
method
for
the
synthesis
of
β,β-di(hetero)aryl-α,α-difluorinated
ketones
using
readily
available
organophosphonium
salts
and
difluoroenol
silyl
ethers
has
been
developed.
This
mild
reaction
features
a
good
functional
group
tolerance,
scaled-up
synthesis,
synthetic
simplicity.
By
taking
advantage
DMSO
as
less-toxic
promoter
solvent
difluoroalkylation
C–P
bond
functionalization,
use
transition-metal
catalysts
sensitive
additives
could
be
avoided.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(17), С. 4569 - 4574
Опубликована: Янв. 1, 2022
A
visible
light
promoted
direct
benzylic
C–H
difluoroalkylation
with
difluoroenoxysilanes
catalyzed
by
Na
2
-eosin
Y
via
a
HAT-ORPC
pathway
has
been
developed,
providing
an
efficient
and
atom-economic
method
for
production
of
α-benzyl-α,α-difluoroketones.
Chinese Journal of Organic Chemistry,
Год журнала:
2022,
Номер
42(11), С. 3562 - 3562
Опубликована: Янв. 1, 2022
Organofluorine
compounds
have
been
widely
applied
in
various
fields
ranging
from
drug
discovery,
clinical
medicines,
agrochemistry,
and
materials
science
to
organic
synthesis,
due
their
special
chemical
physical
properties
when
compared
with
nonfluorinated
analogs.In
the
past
decades,
significant
progress
has
made
development
of
selective
fluorination
fluoroalkylation
for
synthesis
structurally
diverse
fluorine-containing
molecules.Among
them,
α-fluoroalkylated
carbonyl
group
represents
an
important
class
scaffold
components
biologically
active
druglike
compounds.In
this
context,
based
on
use
difluorinated
silyl
enol
ether
(DFSEE)
as
a
unique
fluoroaklylating
reagent,
variety
methods
incorporation
gem-difluoroalkylated
moiety
achieved,
including
aldol,
Mannich,
arylation,
allylation,
protonation,
halogenation,
conjugate
addition,
olefination
reactions.On
other
hand,
DFSEEs
could
also
merge
new
types
reactions
such
radical-type
difluoroalkylation
cascade
reaction
by
virtue
incredible
reactive
flexibility.In
O-site
addition
was
reported,
enabling
construction
versatile
gem-difluoroalkenes.Given
importance
organofluorine
synthetic
potential
these
avenues,
herein,
we
highlight
recent
advances
functionalization
gem-difluorinated
ethers,
which
serve
key
building
blocks
compounds.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(9), С. 1413 - 1418
Опубликована: Апрель 12, 2023
Abstract
Hexafluoroisopropanol
(HFIP)
has
been
extensively
applied
in
organic
synthesis
as
a
versatile
reaction
media.
However,
the
application
of
HFIP
an
catalyst
rarely
studied.
Presented
here,
is
example
HFIP‐catalyzed
Mannich‐type
between
quinoxalin‐2(1
H
)‐ones
and
difluoroenoxysilanes.
The
developed
protocol
tolerates
various
substituents
under
mild
conditions,
providing
divergent
approach
to
construction
difluoro‐substituted
3,4‐dihydroquinoxalin‐2(1
monofluoroquinoxalin‐2(1
51–92%
yields.
magnified
image
