Copper-Catalyzed Chemoselective (Amino)fluorosulfonylation of Hydrocarbons via Intramolecular Fluorine-Atom Transfer
ACS Catalysis,
Год журнала:
2024,
Номер
14(6), С. 4318 - 4328
Опубликована: Март 6, 2024
Sulfonyl
fluorides
have
found
increasing
applications
as
functional
molecules
in
chemistry
and
biology.
We
herein
report
a
copper-catalyzed
atom-economical
access
to
two
categories
of
sulfonyl
through
radical
relay
strategy
the
presence
an
SO2
surrogate.
The
aliphatic
C(sp3)–H
bond
N-fluoro-N-alkyl
sulfonamides
reacted
via
1,5-hydrogen
atom
transfer
(HAT)
process,
affording
alkanesulfonyl
with
proximal
amino
group.
On
other
hand,
utilizing
substrates
containing
proper
C═C
double
resulted
intramolecular
olefin
aminofluorosulfonylation,
allowing
synthesis
fluorosulfonyl-functionalized
pyrrolidines
piperidines
atom-transfer
addition
(ATRA).
Both
reaction
systems
proceeded
under
mild
conditions,
requiring
no
additional
fluorine
source.
Experimental
computational
studies
suggest
that
S–F
coupling
is
likely
achieved
radical-rebound
pathway.
By
taking
advantage
SuFEx
multifunctionality
products,
method
applicable
late-stage
modification
bioactive
compounds,
drug
ligation
chemistry,
organic
synthesis.
Язык: Английский
Electrocatalytic Annulation–Iodosulfonylation of Indole‐Tethered 1,6‐Enynes to Access Pyrrolo[1,2‐a]indoles
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(10)
Опубликована: Янв. 9, 2024
Abstract
We
present
the
first
example
of
electrocatalytic
three‐component
annulation–iodosulfonylation
indole‐tethered
1,6‐enynes
with
arylsulfonyl
hydrazides
and
KI
for
accessing
various
iodosulfonated
pyrrolo[1,2‐
a
]indoles
in
moderate
to
excellent
yields
high
stereospecificity.
This
electrosynthesis
opens
new
avenues
construction
skeleton
good
functional
group
compatibility
under
environmentally
benign
condition.
Based
on
control
experiments
cyclic
voltammetry
data,
we
suggested
plausible
reaction
mechanism
which
included
anodic
oxidation,
homolysis
iodide,
radical
addition,
5
‐
exo
dig
cyclization,
coupling
or
nucleophilic
attack
iodide
ions
cascade.
Язык: Английский
A radical Smiles rearrangement difunctionalization of activated alkenes via desulfonylation and insertion of sulfur dioxide relay strategy
Green Chemistry,
Год журнала:
2024,
Номер
26(11), С. 6774 - 6778
Опубликована: Янв. 1, 2024
A
novel
and
attractive
photochemical
difunctionalization
of
N
-tosyl
acrylamide
for
constructing
alkylsulfonylated
oxindoles
amides
with
excellent
substrate
adaptability
via
a
radical
Smiles
rearrangement
strategy
is
described.
Язык: Английский
Recent advancements in metal‐catalyst‐free multicomponent radical sulfonylation of alkynes
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(43)
Опубликована: Июнь 4, 2024
Vinyl
sulfones
are
crucial
building
blocks
in
synthetic
chemistry
and
core
structural
units
of
pharmaceutically
active
molecules,
thus
extensive
investigations
have
been
conducted
on
the
construction
these
skeletons.
In
contrast
to
classical
approaches,
radical
sulfonylation
alkynes
for
producing
vinyl
has
garnered
considerable
interest
because
its
mild
conditions
high
efficiency.
Radical
sulfonation
typically
begins
with
sulfonyl
attacking
alkynes,
followed
by
further
functionalization.
Moreover,
association
metal-catalyst-free
systems
multicomponent
reactions
(MCRs)
offers
an
environmentally
friendly
pathway
efficiently
constructing
complex
scaffolds
from
readily
available
partners.
However,
there
is
no
comprehensive
review
summarizing
advancements
alkynes.
Hence,
we
provide
a
categorical
overview
based
objects
(hydrosulfonylation,
carbosulfonylation,
aminosulfonylation,
oxysulfonylation,
sulfosulfonylation,
selenosulfonylation,
iodosulfonylation),
along
interpretations
reaction
mechanisms.
Язык: Английский
Oxidant-Assisted Sulfonylation/Cyclization Cascade Synthesis of Alkylsulfonylated Oxindoles via the Insertion of SO2
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(8), С. 5409 - 5422
Опубликована: Апрель 2, 2024
An
oxidant-assisted
tandem
sulfonylation/cyclization
of
electron-deficient
alkenes
with
4-alkyl-substituted
Hantzsch
esters
and
Na2S2O5
for
the
preparation
3-alkylsulfonylated
oxindoles
under
mild
conditions
in
absence
a
photocatalyst
transition
metal
catalyst
is
established.
The
mechanism
studies
show
that
alkyl
radicals,
which
come
from
cleavage
C–C
bond
4-substituted
oxidant
conditions,
subsequently
undergo
situ
insertion
sulfur
dioxide
to
generate
crucial
alkylsulfonyl
radical
intermediates.
This
three-component
reaction
provides
an
efficient
facile
route
construction
alkylsulfonylated
avoids
use
highly
toxic
chlorides
or
hydrazines
as
sources.
Язык: Английский
Copper‐catalyzed radical‐induced annulation‐halo(bi)cyanomethylation of indole‐tethered 1,6‐enynes toward pyrrolo[1,2‐a]indoles
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(17), С. 3578 - 3584
Опубликована: Июнь 18, 2024
Abstract
A
copper‐catalyzed
radical‐induced
annulation‐halocyanomethylation
of
indole‐linked
1,6‐enynes
has
been
established
using
haloacetonitrile
as
radical
precursors,
enabling
the
synthesis
21
cyanomethylated
pyrrolo[1,2‐
a
]indoles
with
yields
ranging
from
42%
to
81%
and
Z
/
E
ratio
up
19:1.
Moreover,
by
adjusting
reaction
temperature,
variation
annulation‐bromobicyanomethylation
process
was
achieved,
resulting
in
production
12
bicyanomethylated
]indole
isomers
41–68%.
The
stereoisomeric
mixture
products
could
be
purified
their
pure
configurations
through
recrystallization.
proposed
mechanism
formulated
series
control
experiments.
Язык: Английский
Photocatalytic Three-Component Radical Sulfonarylation of Alkenes: Preparation of γ-Keto-Sulfone-Substituted Oxindoles
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 16, 2025
A
photocatalytic
radical
sulfonarylation
of
N-arylacrylamides
via
a
three-component
cascade
cyclopropyl
alcohol
ring
opening/sulfur
dioxide
insertion/sulfonyl
addition/cyclization
sequence
has
been
developed.
This
method
employs
alcohols
as
the
precursors
β-carbonyl
alkyl
radicals
and
Na2S2O5
cheap
source
sulfur
dioxide.
By
using
this
procedure,
wide
variety
γ-keto-sulfone-substituted
oxindoles
were
facilely
synthesized.
Язык: Английский
DABCO‐Mediated Photoelectrochemical Three‐Component Sulfonocyclization of 3‐Aza‐1,5‐dienes
Lu-Cai Ding,
Gui-Hong Yang,
Li Luo
и другие.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 2, 2024
Comprehensive
Summary
Herein,
we
report
a
rare
example
of
three‐component
net‐oxidative
sulfonylation
SO
2
surrogate
with
an
oxidatively
activated
radical
precursor
under
mild
and
metal‐
external‐oxidant‐free
conditions.
The
mildness
sustainability
the
reaction
are
enabled
by
photoelectrocatalysis,
3‐aza‐1,5‐dienes,
organotrifluoroborates
1,4‐diazabicyclo[2.2.2]octane
bis(sulfur
dioxide)
adduct
(DABSO)
undergo
sulfonylative
cyclization
to
afford
sulfono
4‐pyrrolin‐2‐ones
in
atom‐economical
manner
broad
substrate
scope
good
functional‐group
tolerance.
protocol
is
amenable
late‐stage
diversification
complex
molecular
architectures
as
well
gram‐scale
synthesis.
Sunlight
could
be
used
light
source,
conducted
all‐solar
mode
using
commercially
available
photovoltaic
panel
generate
electricity
situ
.
Mechanistic
studies
reveal
that
generated
(DABCO),
which
was
generally
innocent
previous
reactions,
functions
electron
shuttle
between
photocatalytic
cycle
reactants.
Язык: Английский
K2S2O8‐Mediated Access to Alkylsulfonated Spiro[4,5] Trienones from N‐Arylpropiolamides with the Insertion of Sulfur Dioxide
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
366(3), С. 488 - 493
Опубликована: Дек. 23, 2023
Abstract
A
four‐component
reaction
of
N
‐arylpropiolamides,
Hantzsch
esters,
Na
2
S
O
5
and
water
via
a
radical
cascade
cyclization
process
with
the
insertion
sulfur
dioxide
mediated
by
K
8
is
reported.
series
alkylsulfonated
spiro[4,5]
trienones
are
prepared
up
to
86%
yield
good
functional
group
tolerance
substrate
applicability.
Preliminary
mechanism
experiments
indicate
that
carbonyl
oxygen
originated
from
water.
Язык: Английский