Organic Letters,
Год журнала:
2024,
Номер
26(21), С. 4514 - 4519
Опубликована: Май 17, 2024
An
efficient
protocol
of
enantioselective
thiolative
azidation
sulfone-tethered
alkenes
via
a
chiral
chalcogenide
catalyzed
electrophilic
reaction
is
disclosed.
A
series
enantioenriched
sulfones
bearing
remote
stereogenic
centers
was
achieved
with
good
yields
and
high
enantioselectivities
linear
unsaturated
cyclic
sulfones.
Mechanistic
studies
revealed
the
importance
sulfone
group
in
improvement
reactivity
enantioselectivity
reaction.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(13)
Опубликована: Фев. 1, 2023
A
method
for
direct
access
to
enantioenriched
benzylic
amides
and
carbamate-protected
primary
benzylamines
by
C-H
functionalization
is
reported.
The
substrate
used
as
limiting
reagent
with
only
a
small
excess
of
the
unactivated
amide
or
carbamate
nucleophile.
enantioselective
intermolecular
dehydrogenative
C-N
bond
formation
enabled
combination
chiral
copper
catalyst,
photocatalyst,
an
oxidant,
it
takes
place
under
mild
conditions,
which
allow
broad
scope.
compatible
late-stage
functionalization,
provides
easy
15
N-labeled
amines
starting
from
cheap
NH4
Cl.
Chemical Communications,
Год журнала:
2023,
Номер
59(26), С. 3821 - 3826
Опубликована: Янв. 1, 2023
In
this
highlight,
we
survey
recent
exciting
advances
in
asymmetric
sulfonylation
by
using
sulfur
dioxide
surrogates,
and
discuss
induction
modes,
reaction
mechanisms,
substrate
scope
opportunities
for
further
studies.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(25)
Опубликована: Апрель 25, 2023
Abstract
Compounds
containing
sulfonyl‐derived
functional
groups
have
received
intensive
attention
owing
to
their
widespread
applications
in
life
science,
pharmaceuticals
and
materials
science.
To
access
this
type
of
compounds,
the
multi‐component
sulfonylation
reactions
relying
on
sulfur
dioxide
(SO
2
)
insertion
strategy
emerged
as
novel
attractive
approaches
past
decade.
The
utilization
SO
surrogates
for
multicomponent
(MCRs)
improved
reaction
flexibility
step
economy.
Moreover,
some
advances
been
achieved
challenging
but
practical
asymmetric
MCRs
construction
high
value‐added
chiral
sulfones.
This
review
aims
summarize
progress
made
involving
from
2019
2022,
point
out
potentials
challenges
field.
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.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(6), С. 3772 - 3780
Опубликована: Март 6, 2023
A
novel
multicomponent
sulfonylation
of
alkenes
is
described
for
the
assembly
various
β-substituted
arylsulfones
using
cheap
and
easily
available
K2S2O5
as
a
sulfur
dioxide
source.
Of
note,
procedure
does
not
need
any
extra
oxidants
metal
catalysts
exhibits
relatively
wide
substrate
scope
good
functional
group
compatibility.
Mechanistically,
an
initial
arylsulfonyl
radical
formed
involving
insertion
with
aryl
diazonium
salt,
followed
by
alkoxyarylsulfonylation
or
hydroxysulfonylation
alkenes.
Organic Letters,
Год журнала:
2023,
Номер
25(31), С. 5916 - 5921
Опубликована: Июль 27, 2023
A
copper-catalyzed
trifluoromethylthio-arylsulfonylation
between
1,3-enynes,
AgSCF3,
aryldiazonium
tetrafluoroborates,
and
SO2
(from
SOgen)
is
presented,
which
could
introduce
sulfone,
SCF3,
allene
moieties
into
one
molecule
simultaneously.
This
strategy
features
mild
reaction
conditions,
good
substrate
compatibility,
excellent
regioselectivity.
The
products
obtained
have
the
potential
for
further
conversion
other
valuable
compounds.
Initial
investigations
mechanism
suggest
that
it
may
proceed
via
a
radical
pathway.
Notably,
SOgen
was
proven
as
uniquely
effective
surrogate
in
this
transformation.
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.
Organic Letters,
Год журнала:
2024,
Номер
26(31), С. 6652 - 6657
Опубликована: Июль 26, 2024
We
report
a
visible-light-promoted
cyclization/sulfonylation
cascade
of
N-heterocycles
with
thianthrenium
salts
using
DABSO
as
the
SO2
surrogate.
This
method
features
excellent
functional
group
tolerance,
wide
substrate
scope,
and
late-stage
elaboration
bioactive
relevant
molecules.
Mechanistic
investigations
reveal
that
photoactive
electron
donor–acceptor
(EDA)
complexes
between
DABCO
are
capable
generation
aryl
radicals,
which
induce
following
insertion
by
attacking
DABSO,
thus
triggering
key
radical
cyclization
step.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(6), С. 1678 - 1684
Опубликована: Янв. 1, 2024
This
method
allows
for
the
enantioselective
synthesis
of
β-azide
sulfones
via
iron-catalyzed
vicinal
azide-sulfonylation
acrylamides.
It
makes
first
instance
achieving
asymmetric
construction
through
iron
catalysis
with
SO
2
insertion.
Abstract
A
novel
catalytic
system
for
radical
cross‐coupling
reactions
based
on
copper
and
chiral
Pyridyl‐bis(imidazole)
(PyBim)
ligands
is
described.
It
overcomes
the
challenges
of
chemoselectivity
enantioselectivity,
achieving
a
highly
enantioselective
vicinal
sulfonyl‐esterification
reaction
alkenes
involving
sulfur
dioxide.
This
strategy
involves
use
earth‐abundant
metal
catalyst,
mild
conditions,
broad
range
substrates
(84
examples),
high
yields
(up
to
97%
yield),
exceptional
control
over
enantioselectivity.
The
compatible
with
different
types
precursors,
including
O
‐acylhydroxylamines,
cycloketone
oxime
esters,
aryldiazonium
salts,
drug
molecules.
Chiral
ligand
PyBim
identified
as
particularly
effective
in
desired
Mechanistic
studies
reveal
that
copper/PyBim
plays
vital
role
C─O
coupling,
employing
an
outer‐sphere
model.
In
addition,
side
arm
effect
observed.
