Angewandte Chemie,
Год журнала:
2023,
Номер
135(46)
Опубликована: Окт. 2, 2023
Abstract
This
research
explores
the
enantioselective
hydrosulfonylation
of
various
α,β‐unsaturated
carbonyl
compounds
via
use
visible
light
and
redox‐active
chiral
Ni‐catalysis,
facilitating
synthesis
enantioenriched
α‐chiral
sulfones
with
remarkable
enantioselectivity
(exceeding
99
%
ee).
A
significant
challenge
entails
enhancing
reactivity
between
metal‐coordinated
moderate
electrophilic
sulfonyl
radicals,
aiming
to
minimize
background
reactions.
The
success
our
approach
stems
from
two
distinctive
attributes:
1)
Cl‐atom
abstraction
employed
for
radical
generation
chlorides,
2)
single‐electron
reduction
produce
a
key
enolate
Ni‐complex.
latter
process
appears
enhance
feasibility
radical's
addition
electron‐rich
radical.
An
in‐depth
investigation
into
reaction
mechanism,
supported
by
both
experimental
observations
theoretical
analysis,
offers
insight
intricate
process.
Moreover,
versatility
methodology
is
highlighted
through
its
successful
application
in
late‐stage
functionalization
complex
bioactive
molecules,
demonstrating
practicality
as
strategy
producing
sulfones.
Organic Letters,
Год журнала:
2024,
Номер
26(15), С. 3321 - 3325
Опубликована: Апрель 10, 2024
Asymmetric
sulfonylation
from
a
reaction
of
cyclopropan-1-ol,
sulfur
dioxide,
and
1-(alkynyl)naphthalen-2-ol
in
the
presence
catalytic
amount
organocatalyst
at
room
temperature
is
developed.
Axially
chiral
(S)-(E)-1-(1-(alkylsulfonyl)-2-arylvinyl)naphthalen-2-ols
are
generated
moderate
to
good
yields
with
excellent
enantioselectivity
regioselectivity
under
mild
conditions.
During
this
transformation,
γ-keto
sulfinate
situ
cyclopropan-1-ol
dioxide
acts
as
key
intermediate.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(25), С. 16996 - 17002
Опубликована: Июнь 14, 2024
A
highly
regio-
and
enantioselective
hydrosulfonylation
using
commercially
available
sodium
sulfinates
is
reported,
providing
the
first
direct
asymmetric
rhodium-catalyzed
of
allenes/alkynes
to
synthesize
chiral
allylic
sulfones.
Ligand
screening
studies
demonstrated
indispensable
role
C1-symmetric
P,N-ligand
(Rax,S,S)-StackPhim
for
achieving
both
high
regioselecitivity
(>20:1)
enantioselectivity
(up
97%
ee).
Notably,
operationally
simple
method
mild
conditions
allow
rapid
preparation
sulfones
with
a
wide
scope
functional
groups.
Moreover,
use
tert-butyldimethylsilyloxymethanesulfinate
enables
collective
synthesis
various
sulfone
derivatives
after
transformations
protected
hydroxymethyl
product.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(46)
Опубликована: Окт. 2, 2023
This
research
explores
the
enantioselective
hydrosulfonylation
of
various
α,β-unsaturated
carbonyl
compounds
via
use
visible
light
and
redox-active
chiral
Ni-catalysis,
facilitating
synthesis
enantioenriched
α-chiral
sulfones
with
remarkable
enantioselectivity
(exceeding
99
%
ee).
A
significant
challenge
entails
enhancing
reactivity
between
metal-coordinated
moderate
electrophilic
sulfonyl
radicals,
aiming
to
minimize
background
reactions.
The
success
our
approach
stems
from
two
distinctive
attributes:
1)
Cl-atom
abstraction
employed
for
radical
generation
chlorides,
2)
single-electron
reduction
produce
a
key
enolate
Ni-complex.
latter
process
appears
enhance
feasibility
radical's
addition
electron-rich
radical.
An
in-depth
investigation
into
reaction
mechanism,
supported
by
both
experimental
observations
theoretical
analysis,
offers
insight
intricate
process.
Moreover,
versatility
methodology
is
highlighted
through
its
successful
application
in
late-stage
functionalization
complex
bioactive
molecules,
demonstrating
practicality
as
strategy
producing
sulfones.
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.
ACS Catalysis,
Год журнала:
2024,
Номер
14(9), С. 6513 - 6524
Опубликована: Апрель 13, 2024
Efficient
synthesis
of
sulfonamides
has
long
been
pursued
by
chemists
due
to
their
frequent
occurrence
in
pharmaceuticals,
especially
anti-inflammatory
medicines.
The
traditional
assembly
from
sulfonyl
chlorides
and
amines,
as
well
the
recently
developed
one-step
involving
sulfur
dioxide,
still
faces
challenges
such
poor
substrate
compatibility
and/or
stringent
reaction
conditions.
Herein,
we
present
a
strategy
for
situ
generation
sulfamoyl
radicals
modular
both
alkenyl
alkyl
with
wide
applicability
(>100
examples),
mild
conditions,
easily
accessible
starting
materials.
This
method
is
successfully
applied
late-stage
modification
drug
molecules
(23
molecule
naratriptan,
15N-labeling
sulfonamides.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(29), С. 5868 - 5885
Опубликована: Янв. 1, 2024
The
importance
of
sulfonyl-group-containing
compounds,
such
as
sulfonamides,
sulfones,
sulfinate
esters,
and
sulfonyl
fluorides,
in
pharmaceuticals,
bioactive
molecules,
natural
products
cannot
be
overstated.
new
development
palladium-catalyzed
sulfonylation
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.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 20, 2025
For
the
first
time,
a
photoredox-catalyzed
alkoxycarbonylation/tricyclization
reaction
was
developed
by
employing
readily
accessible
enediynes
and
alkyloxalyl
chlorides
as
starting
materials,
enabling
synthesis
of
ester-substituted
polycyclic
N-heteroaromatics
under
mild
conditions
through
radical-mediated
mechanism.
This
photocatalytic
strategy
is
notable
for
its
exceptional
compatibility
with
diverse
functional
groups,
scalability,
efficiency
in
formation
rings
chemical
bonds.
Notably,
continuous
flow
photocatalysis
technology
markedly
improved
these
reactions
compared
to
equivalent
batch
reactions,
efficiently
decreasing
times
merely
40
min.
