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.
Chemical Communications,
Год журнала:
2024,
Номер
60(56), С. 7228 - 7231
Опубликована: Янв. 1, 2024
A
visible-light-induced
K
2
S
O
8
-promoted
cascade
sulfonation/cyclization
reaction
to
afford
a
series
of
sulfonated
quinolino[2,1-
b
]quinazolinones
has
been
developed
under
mild
conditions.
Organic Letters,
Год журнала:
2023,
Номер
25(50), С. 9014 - 9019
Опубликована: Дек. 8, 2023
Photoinduced
generation
of
phosphoranyl
radicals
offers
a
versatile
strategy
to
access
variety
synthetically
valuable
radicals.
A
long-standing
challenge
remains
in
the
regulation
radical
undergo
α-scission
pathway,
although
β-scission
mode
has
been
intensively
studied.
We
herein
developed
an
unprecedented
protocol
for
selective
P(OH)R3
intermediate
under
photocatalytic
conditions.
This
efficient
P-C
bond
cleavage
via
successfully
utilized
alkylation/fluoroalkylation
alkenes.
Green Chemistry,
Год журнала:
2024,
Номер
26(4), С. 2280 - 2289
Опубликована: Янв. 1, 2024
A
visible-light-enabled
catalyst-free
[3
+
2]
cycloaddition/N–N
bond
cleavage/intramolecular
C–N
formation
cascade
process
to
access
2,3-difunctionalized
pyridines
was
developed.
Organic Letters,
Год журнала:
2024,
Номер
26(27), С. 5799 - 5804
Опубликована: Июль 2, 2024
Herein,
we
disclose
a
photoinduced
radical
cascade
cyclization
of
alkynes
with
sulfinates
via
novel
EDA
complex
for
the
synthesis
various
3-sulfonylindoles
and
vinyl
sulfone
oxindoles,
which
are
crucial
motifs
in
medicinal
biological
chemistry.
The
reaction
proceeds
under
mild,
photocatalyst-
transition-metal-free
conditions,
featuring
operational
simplicity,
broad
substrate
scope,
easy
scalability.
Mechanistic
studies
reveal
that
is
initiated
intermolecular
charge
transfer
from
to
N-sulfonamides,
generating
sulfonyl
followed
by
an
N-centered
radical,
thus
enabling
process.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(17), С. 12159 - 12169
Опубликована: Авг. 16, 2024
An
efficient
and
high-selectivity
approach
for
the
divergent
synthesis
of
β-sulfinyl
alkenylsulfones
(E)-vinyl
sulfones
from
alkynes
TsCN
is
described.
A
series
disulfurized
products
were
constructed
under
mild
conditions
in
absence
transition
metals.
This
transformation
featured
excellent
regio-
stereoselectivity,
good
functional
group
compatibility,
broad
substrate
scope.
The
copper(I)-catalyzed
sulfonation
with
that
affords
to
yields
was
also
developed.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 26, 2024
A
photoredox-catalyzed
aminolactonization
of
unsaturated
carboxylic
acids
was
achieved
using
N-aminopyridinium
salts
as
the
amino
radical
precursor.
The
transformation
features
mild
conditions
and
a
remarkably
broad
substrate
scope,
offering
an
efficient
approach
to
construct
wide
range
4-sulfonamino
3,4-dihydroisocoumarins.
Mechanistic
studies
indicate
that
reaction
proceeds
via
distinctive
salt-promoted
electrophilic
amination
2-styrylbenzoic
acids.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(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
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 10, 2024
Comprehensive
Summary
Two
reaction
modes
for
metal‐free
[3
+
2]
cyclization
of
N
‐aminopyridinium
derivatives
with
β
‐alkoxyvinyl
trifluoromethylketones
have
been
described
through
selective
C—O
or
C—O/C—C
bond
cleavage.
This
strategy
can
also
be
extended
to
the
enaminones
and
bromoalkynes.
A
broad
range
‐aminopyridinium,
‐aminoquinolinium,
‐aminoisoquinolinium
salts
are
well
tolerated,
enabling
divergent
synthesis
trifluoroacylated,
non‐substituted,
acylated,
brominated
pyrazolo[1,5‐
a
]pyridine
(62
examples).
