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 Chemistry Frontiers,
Год журнала:
2024,
Номер
11(7), С. 2027 - 2032
Опубликована: Янв. 1, 2024
A
redox-neutral
strategy
for
C(sp
3
)–H
phosphorylation
is
developed
via
photoinduced
LMCT,
where
the
reaction
proceeds
through
radical
addition
to
chlorophosphines
form
an
R
P–Cl˙
and
ultimately
concluded
by
single-electron
reduction.
Green Chemistry,
Год журнала:
2024,
Номер
26(11), С. 6578 - 6583
Опубликована: Янв. 1, 2024
Using
sulfinic
acid
as
a
sulfonyl
source,
we
have
developed
light-promoted
photocatalyst-free
alkene
hydrosulfonylation
reaction
without
any
additives.
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.
Organic Letters,
Год журнала:
2023,
Номер
25(50), С. 8970 - 8974
Опубликована: Дек. 12, 2023
The
progress
of
efficient
and
sustainable
approaches
for
decarboxylative
coupling
reactions
is
synthetically
appealing
due
to
the
structural
diversity,
lack
toxicity,
widespread
commercial
accessibility
carboxylic
acids.
However,
decarboxylation
reaction
still
encounters
challenges
related
utilization
oxidants,
catalysts,
prefunctionalization
conditions.
We
report
herein
a
mild
method
that
facilitates
direct
electron
transfer
between
alkyl
acids
excited-state
substrates
C-H
alkylation
quinoxalin-2(1H)-ones
without
involvement
any
catalyst
or
additive.
Organic Letters,
Год журнала:
2024,
Номер
26(23), С. 4926 - 4931
Опубликована: Июнь 4, 2024
N-centered
nucleophilicity
increases
upon
alkylation,
and
thus
selective
partial
alkylation
of
ammonia
primary
amines
can
be
challenging:
Poor
selectivity
overalkylation
are
often
observed.
Here
we
introduce
N-aminopyridinium
salts
as
surrogates
for
the
synthesis
secondary
via
self-limiting
chemistry.
Readily
available
N-aryl-N-aminopyridinium
engage
in
N-alkylation
situ
depyridylation
to
afford
aryl-alkyl
without
any
products.
The
method
overcomes
classical
challenges
amine
by
accomplishing
transient,
highly
nucleophilic
pyridinium
ylide
intermediates
applied
context
complex
molecular
scaffolds.
These
findings
establish
synthons
synthetic
chemistry
a
strategy
control
extent
alkylation.
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.
ACS Catalysis,
Год журнала:
2024,
Номер
14(16), С. 12282 - 12296
Опубликована: Авг. 2, 2024
A
visible-light-photocatalyzed
hydrosulfonylation
of
unactivated
alkenes
with
symmetrical
disulfones
using
2,4,6-triisopropylthiophenol
as
a
hydrogen
atom
donor
(H-D)
has
been
developed.
Generation
two
sulfonyl
radicals
from
via
activation
visible
light
photocatalysis
is
involved.
Mechanistic
studies
rule
out
that
are
generated
disulfone
an
energy
transfer
mechanism
previously
found
for
lower
oxidation
state
sulfur–sulfur-based
reactants
(i.e.,
thiosulfonates
and
disulfides).
Instead,
mimic
process
occurs.
This
involves
photoinduced
electron
(PET)
oxidative
quenching
the
excited
photocatalyst
(*PC)
disulfone,
which
generates
radical
sulfinate
byproduct,
followed
by
reduction
oxidized
(PC•+)
this
byproduct
(SET)
generating
second
(PC).
The
reaction
can
be
performed
in
dimethyl
carbonate
at
room
temperature,
features
broad
functional
group
compatibility,
allows
easy
recycling
disulfide
provided
2,4,6-trisubstituted
thiophenol
used
H-D.
compared
state-of-the-art
green
metrics.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(47)
Опубликована: Авг. 10, 2024
Abstract
The
functionalization
of
pyridines
is
crucial
for
the
rapid
construction
and
derivatization
agrochemicals,
pharmaceuticals,
materials.
Conventional
approaches
have
primarily
focused
on
ortho
‐
para
‐positions,
while
achieving
precise
meta‐selective
functionalization,
particularly
at
C5
position
in
substituted
pyridines,
remains
a
formidable
challenge
due
to
intrinsic
electronic
properties
pyridines.
Herein,
we
present
new
strategy
meta
C5‐selective
C−H
sulfonylation
N
‐amidopyridinium
salts,
which
employs
transient
enamine‐type
intermediate
generated
through
nucleophilic
addition
salts.
This
process
harnesses
power
electron
donor‐acceptor
complexes,
enabling
high
selectivity
broad
applicability,
including
complex
bearing
valuable
sulfonyl
functionalities
under
mild
conditions
without
need
an
external
photocatalyst.
remarkable
selectivity,
combined
with
applicability
late‐stage
significantly
expands
toolbox
pyridine
unlocking
access
previously
unattainable
‐sulfonylated
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(9), С. 2003 - 2007
Опубликована: Март 12, 2024
Abstract
A
DBU‐promoted
[3+2]
cyclization/retro‐Mannich
cascade
reaction
of
N
‐aminoisoquinolinium
and
‐aminoquinolinium
derivatives
with
para
‐quinone
methides
has
been
established,
employing
a
C=C
double
bond
cleavage.
broad
range
salts,
are
well
tolerated,
providing
the
corresponding
rearrangement
products.
Moreover,
scaled‐up
reactions
diverse
derivatizations
products
were
also
investigated
discussed.
Abstract
A
convenient
and
sustainable
method
for
synthesizing
sulfonyl‐containing
compounds
through
a
catalyst‐free
aqueous‐phase
hydrosulfonylation
of
alkenes
alkynes
with
sulfonyl
chlorides
under
visible
light
irradiation
is
presented.
Unactivated
alkenes,
electron‐deficient
alkyl
aryl
can
be
hydrosulfonylated
various
at
room
temperature
excellent
yields
geometric
selectivities
by
using
tris(trimethylsilyl)silane
as
hydrogen
atom
donor
silyl
radical
precursor
to
activate
chlorides.
Mechanistic
studies
revealed
that
the
photolysis
in
aqueous
solution
produce
crucial
success
this
reaction.
