Three-Component Sulfonylation and Heteroannulation Enabled by 3-Fold Defluorofunctionalization of Trifluoromethyl Enones
Shu-Ji Gao,
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Xueying Huang,
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M Kellis
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et al.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 23, 2025
Trifluoromethyl
enone
emerges
as
a
versatile
and
multifaceted
building
block
in
organic
synthesis.
A
defluorinative
heterocyclization
reaction
of
readily
available
β,β-ditrifluoromethylated
enones
biocompatible
sodium
sulfinates
has
been
developed
for
the
modular
synthesis
densely
functionalized
furans
with
regio-defined
C2,4-bissulfonyl
C3-trifluoromethyl
substitutions.
This
three-component
method
proceeds
through
sequential
sulfonylation
intramolecular
O-cyclization,
enabling
assembly
one
furan
ring,
formation
C-SO2/C–O
bonds,
cleavage
three
C(sp3)-F
bonds
one-pot
manner
under
transition
metal-free
conditions.
Moreover,
obtained
product
can
further
react
benzyne
precursor
to
generate
1,4-epoxynaphthalene
Diels–Alder
cycloaddition.
The
is
also
distinguished
by
its
broad
substrate
scope,
excellent
functional
group
tolerance,
scalability.
Language: Английский
Perfluoroalkyl Editing of Fluoroalkynes: Chemo-, Regio-, and Stereoselective Synthesis of (E)-(2-Amino-fluoroalkenyl)pyrimidines
M Kellis,
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Ming-Yao Tang,
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Tong Qian
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et al.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 26, 2025
A
chemo-,
regio-,
and
stereoselective
condensation
reaction
of
perfluoroalkyl
alkynes
(PFAAs),
(CH2O)n,
(NH4)2CO3
through
the
cleavage
five
inert
C(sp3)-F
bonds
at
three
distinct
carbon
sites,
thereby
establishing
an
unprecedented
platform
for
synthesizing
structurally
unique
(E)-(2-amino-fluoroalkenyl)pyrimidines,
is
first
developed.
Remarkably,
this
features
mild
conditions,
good
compatibility
with
various
functional
groups,
excellent
E-stereoselectivity,
late-stage
modification
complex
molecules,
scalability,
versatile
synthetic
transformations
resulting
heterocyclic
compounds.
Language: Английский
[4+2] Defluorocycloaddition of Perfluoroalkyl Alkynes and Benzylamines: Synthesis of meta-Fluoroalkylated Pyridin-4-amines
Xueying Huang,
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Jiawei Chen,
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D.‐L. CHEN
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et al.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 28, 2025
Pyridines
represent
privileged
heterocycles,
and
the
ability
to
produce
fluorinated
pyridines
from
polyfluorinated
substances
through
selective
defluorofunctionalization
is
a
new
addition
their
synthesis.
Herein,
an
unprecedented
formal
[4+2]
defluorocycloaddition
of
perfluoroalkyl
alkynes
benzylamines
under
metal-free
conditions
described.
By
leveraging
functionalization
four
C(sp3)–F
bonds
on
two
vicinal
sterically
hindered
carbons
alkynes,
diverse
array
meta-fluoroalkylated
pyridin-4-amines
were
synthesized
with
good
functional
group
tolerance.
The
mechanistic
studies
revealed
sequence
hydroamination,
successive
defluorination,
6π-electrocyclization,
aromatization,
amination.
Language: Английский
Water-Involved 1,3-Aminoxylation of Fluoroalkenes: Chemo-, Regio-, and Stereoselective Synthesis of β-Fluoroacyl Vinylamines
Chi Zhang,
No information about this author
Xueying Huang,
No information about this author
Shu-Ji Gao
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et al.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 9, 2025
Perfluoroalkyl
alkenyl
iodides
(PFAIs)
are
emerging
as
highly
reactive,
storage-stable,
and
multifunctional
fluoroalkyl-bearing
reagents,
facilitating
the
manufacture
of
value-added
organofluorides
through
multi-halo-functionalization.
Herein,
we
developed
a
water-involved
1,3-aminoxylation
PFAIs
with
sulfonamides
for
chemo-,
regio-,
Z-stereoselective
synthesis
valuable
β-fluoroacyl
vinylamines.
This
reaction
proceeded
via
sequential
deiodoamination
defluoroxylation
process
under
transition-metal-free
conditions,
featuring
broad
substrate
scope
good
functional
group
tolerance.
Compared
to
reported
methods,
some
drawbacks,
such
multistep
manipulation,
harsh
need
expensive
catalysts,
use
toxic/sensitive
could
be
eliminated.
Furthermore,
synthetic
potential
this
method
was
demonstrated
scale-up
synthesis,
postfunctionalization
complex
molecules,
ready
transformation
products.
Language: Английский
Diastereoselective Formal [3+3] Cascade Cyclization towards Fused 4‐Fluoroalkylated 3,4‐Dihydro‐2H‐pyrans via Copper Catalysis
Weigao Hu,
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Jiawen Yin,
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Zhiyong Li
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et al.
Chinese Journal of Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 25, 2025
Comprehensive
Summary
The
cycloaddition
and
annulation
reactions
offer
a
powerful
method
toward
various
important
substituted
3,4‐dihydro‐2
H
‐pyran
architectures.
Nevertheless,
the
transformation
for
preparing
fused‐polycyclic
ones
still
remains
challenging
yet
highly
desirable
until
now.
Herein,
we
report
novel
formal
[3+3]
cascade
cyclization
reaction
to
provide
lactam‐fused
4‐fluoroalkylated
3,4‐dihydropyran
skeletons
bearing
three
contiguous
tertiary
carbon
centers
via
copper
catalysis.
Of
note,
these
annulations
proceeded
in
an
exclusively
diastereoselective
manner
through
successive
inert
C(sp
2
)‐Cl
3
)‐H
functionalization,
which
exhibited
site‐selectivity
stereoselectivity.
Additionally,
evaluations
on
biological
activities
of
obtained
products
revealed
that
several
display
inhibitory
activity
against
Siha
H1975
cancer
cell
lines.
Language: Английский