Organic Letters,
Год журнала:
2021,
Номер
23(24), С. 9526 - 9532
Опубликована: Дек. 3, 2021
A
TfOH-promoted
synthesis
of
fluorinated
polyfused
heterocycles
via
the
cascade
cyclization
azadienes
and
difluoroenoxysilanes
has
been
developed,
leading
to
facile
construction
benzofuro[3,2-b]pyridines,
5H-indeno[1,2-b]pyridines,
5,6-dihydrobenzo[h]quinolines.
This
one-pot
formal
[4
+
2]
approach
involves
1,4-difluoroalkylation,
desulfonylation,
cyclization,
dehydrated
dehydrofluorinated
aromatization
represents
first
application
difluoroenoxysilane
in
transformations.
Furthermore,
this
methodology
is
highlighted
by
three
fluoro
analogues
bioactive
molecules
with
potent
topoisomerase
inhibitory
activities.
Organic Letters,
Год журнала:
2020,
Номер
22(22), С. 9010 - 9015
Опубликована: Ноя. 4, 2020
A
poly
trifluoromethylated
chiral
spirocyclic
phosphoric
acid
was
developed
and
employed
with
hexafluoroisoproyl
alcohol
(HFIP)
to
render
the
catalytic
asymmetric
Mukaiyama-Mannich
reaction
of
difluoroenoxysilanes
in
situ
formed
ketimines.
This
unique
multiple-fluorine
system
provides
rapid
access
difluoromethylated
tetrasubstituted
stereocenters
isoindolones
wide
substrate
scope
under
mild
conditions.
Further
synthetic
transformations
enantioenriched
CF2H-isoindolones
CF2-decorated
fused
were
also
implemented
good
efficiency.
Nature Communications,
Год журнала:
2020,
Номер
11(1)
Опубликована: Окт. 30, 2020
Abstract
Alkene
hydrodifluoroalkylation
is
a
fruitful
strategy
for
synthesizing
difluoromethylated
compounds
that
are
interesting
developing
new
medicinal
agents,
agrochemicals,
and
advanced
materials.
Whereas
the
anti-Markovnikov
to
linear-type
products
developed,
employing
radical-based
processes,
Markovnikov
synthesis
of
branched
adducts
remains
unexplored.
Herein,
we
describe
acid-catalyzed
processes
involving
carbocation
intermediates
as
promising
secure
regioselectivity.
Accordingly,
mono-,
di-,
tri-,
tetrasubstituted
alkenes
using
difluoroenoxysilanes,
catalyzed
by
Mg(ClO
4
)
2
·6H
O,
achieved.
This
allows
diversity-oriented
α,α-difluoroketones
with
quaternary
or
tertiary
carbon
at
β-position
otherwise
difficult
access.
The
method
applied
modification
natural
drug
derivatives.
resulting
α,α-difluorinated
ketones
could
be
converted
corresponding
esters
alcohols,
organofluorine
featuring
CF
H
Ph
moiety.
Mechanistic
studies
support
O
functions
hidden
Brønsted
acid
catalyst.
Chemical Communications,
Год журнала:
2020,
Номер
56(66), С. 9469 - 9472
Опубликована: Янв. 1, 2020
A
photoredox-catalyzed
three-component
reaction
of
aryldiazonium
tetrafluoroborates
with
sodium
metabisulfite
and
2,2-difluoro
enol
silyl
ethers
is
described.
By
using
as
the
source
sulfur
dioxide,
this
method
provides
an
elegant
access
to
α,α-difluoro-β-ketosulfones
in
moderate
good
yields
under
mild
conditions,
features
a
broad
substrate
scope
wide
functional
group
tolerance.
Both
difluoromethyl
sulfone
moiety
can
be
introduced
single
step.
Based
on
experimental
results,
single-electron
transfer
pathway
proposed
insertion
dioxide.
Organic Letters,
Год журнала:
2020,
Номер
22(19), С. 7747 - 7751
Опубликована: Сен. 18, 2020
A
general
method
for
site-selective
difluoroalkylation
of
alkyl
carboxylic
redox
esters
with
difluoroenoxysilanes
through
photoredox-catalyzed
decarboxylative
reaction
has
been
developed.
The
can
also
be
extended
to
aliphatic
amine
derived
pyridinium
salts.
This
the
advantages
high
efficiency,
mild
conditions,
and
broad
substrate
scope,
including
primary,
secondary,
sterically
hindered
tertiaryl
substrates,
providing
a
practical
route
applications
in
organic
synthesis
pharmaceutical
studies.
Advanced Synthesis & Catalysis,
Год журнала:
2020,
Номер
362(22), С. 4763 - 4793
Опубликована: Сен. 23, 2020
Abstract
Enantioenriched
fluorinated
α‐
and
β‐amino
acids
are
often
encountered
in
numerous
pharmaceuticals
bioactive
molecules,
also
of
great
importance
as
probes
PET
NMR
for
studying
the
behavior
enzymes
incorporation
into
peptides
drug
candidates.
Among
various
synthetic
strategies
developed,
catalytic
enantioselective
synthesis
proves
to
be
one
most
facile
powerful
protocols
construct
such
privileged
structures.
The
past
decade
has
witnessed
considerable
progress
construction
chiral
acid
derivatives
with
structural
diversity.
In
this
review,
we
summarize
these
impressive
achievements
according
bond‐forming
way
or
acids,
respectively,
underline
remaining
challenges.
This
information
would
provide
important
guidance
some
inspiration
researchers
engaged
organic
fluorine
medicinal
chemistry.
magnified
image
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(42), С. 18500 - 18504
Опубликована: Июль 11, 2020
An
enantioselective
bifunctional
squaramide-catalyzed
detrifluoroacetylative
alkylation
reaction
has
been
developed
under
electrochemical
conditions.
The
unified
strategy
based
on
this
key
tandem
methodology
divergently
explored
for
the
asymmetric
synthesis
of
fluorine-containing
target
molecules
with
good
stereocontrol
(up
to
95
%
ee).
Furthermore,
catalytic
combines
benefits
electrosynthesis
and
organocatalysis
preparation
biologically
relevant
products
containing
C-F
tertiary
stereogenic
centers.
Organic Letters,
Год журнала:
2021,
Номер
23(7), С. 2670 - 2675
Опубликована: Март 16, 2021
With
Ph3P+CF2COO–
or
TMSCF2Br
as
the
difluorocarbene
sources,
a
facile
metal-free
cycloaddition
between
heteroconjugated
alkenes
and
was
developed
for
highly
convergent
synthesis
of
novel
difluorinated
heterocyclics,
including
gem-difluorinated
azetidines
2,3-dihydrobenzofurans.
The
features
high
reactivity
regioselectivity,
well
good
tolerance
various
electron-donating
electron-withdrawing
substituents
on
azaheptafulvenes
o-quinone
methides.
