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.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 14, 2024
Photosynthesis,
converting
sustainable
solar
energy
into
chemical
energy,
has
emerged
as
a
promising
craft
to
achieve
diverse
organic
transformations
due
its
mild
reaction
conditions,
sustainability,
and
high
efficiency.
The
synthesis
of
sulfonated
compounds
drawn
significant
attention
in
the
pharmaceuticals,
agrochemicals,
materials
industries
unique
structure
electronic
properties
sulfonyl
groups.
Over
past
decades,
many
photocatalytic
sulfonylation
reactions
have
been
developed.
In
this
review,
recent
advances
photocatalyzed
reviewed
since
2020,
with
primary
focus
on
discussing
design
mechanism.
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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(26)
Опубликована: Апрель 15, 2024
We
report
a
user-friendly
approach
for
the
decarboxylative
formation
of
stereodefined
and
complex
tri-
tetra-substituted
olefins
from
vinyl
cyclic
carbonates
amines
as
radical
precursors.
The
protocol
relies
on
easy
photo-initiated
α-amino-radical
followed
by
addition
onto
double
bond
substrate
resulting
in
sequence
involving
carbonate
ring-opening,
relay,
CO
Organic Letters,
Год журнала:
2024,
Номер
26(26), С. 5577 - 5581
Опубликована: Июнь 24, 2024
A
visible-light-mediated
catalyst-
and
additive-free
method
for
radical
ring-opening
fluorosulfonylation
of
methylenecyclobutanols
is
reported.
Sulfuryl
chlorofluoride
acts
as
a
FSO
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(14), С. 1599 - 1605
Опубликована: Март 13, 2024
Comprehensive
Summary
Functionalized
free
radical
addition/cyclization
reactions
represent
an
efficient
way
for
introducing
new
functionality
or
coupling
fragments
to
molecules.
Ynones
are
good
regional
selectivity
acceptors
in
organic
synthesis,
and
many
of
bio‐relevant
cyclic
compounds
could
be
easily
obtained
by
direct
cyclization
reaction.
Here,
we
report
a
photocatalytic
cascade
addition
biaryl
ynones,
the
divergent
synthesis
privileged
carbon
cycles.
Additionally,
further
transformation
multi‐functional
group
product
into
variety
other
derivatives
demonstrates
synthetic
value
this
developed
method.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(44)
Опубликована: Июль 22, 2024
Sulfur(VI)-based
functional
groups
are
popular
scaffolds
in
a
wide
variety
of
research
fields
including
synthetic
and
medicinal
chemistry,
as
well
chemical
biology.
The
growing
interest
sulfur(VI)-containing
molecules
has
motivated
the
scientific
community
to
explore
new
methods
synthesize
modify
them.
Here,
photocatalysis
plays
key
role
granting
access
types
reactivity
under
mild
reaction
conditions.
In
this
Perspective,
we
present
selection
works
reported
last
six
years
focused
on
photocatalytic
assembly
sulfones,
sulfonamides,
sulfoximines.
We
addressed
intermediates
for
each
transformation,
while
discussing
limitations
strength
points
protocols.
Future
directions
field
finally
presented.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(20), С. 5784 - 5790
Опубликована: Янв. 1, 2024
The
radical
cascade
cyclization
of
vinyl-tethered
alkenes
has
become
a
promising
tool
for
rapidly
assembling
nonbenzene-fused
cyclic
skeletons
via
the
cracking
alkenyl
C–H
bonds,
but
this
approach
been
limited
to
generate
five-membered
rings.
The
enantioselective
ring-opening
reactions
of
methylenecyclopropanes
(MCPs)
involving
C–C
bond
activation
via
oxidative
addition
transition
metals
have
been
rarely
reported.
Here,
we
disclose
a
Pd/Cu-catalyzed
enantio-
and
regioselective
coupling
between
cyclic
imino
esters
MCPs
to
produce
α-allylated
2H-pyrrole
derivatives.
In
this
reaction,
azomethine
ylide
formed
by
chiral
copper
catalyst
with
ketimine
ester
would
serve
as
nucleophile
react
activated
palladium
catalysis.
This
bimetallic
system
exhibited
broad
substrate
scope
high
regio-
enantioselectivities.
JACS Au,
Год журнала:
2025,
Номер
5(2), С. 913 - 921
Опубликована: Фев. 11, 2025
Rapid
access
to
highly
functional
allylated
BCP
synthons
can
be
achieved
with
good
selectivity
and
yield
through
a
radical,
three-component
reaction
(3CR)
regime
using
various
combinations
of
radical
precursors
vinyl-appended
heterocycles
acting
as
versatile
modular
precursors.
This
practical
process
combines
mild
operating
conditions,
wide
scope
partners,
the
ability
diversify
functionalized
allylic
scaffolds
further
allyl
other
groups
synthetic
branching
points.
The
developed
protocol
allows
structural
alteration
increases
molecular
complexity
late-stage
drug
modifications
conjugation
approaches.
Mechanistic
probes
demonstrate
that
3CR
is
initiated
by
selective,
light-promoted
addition
[1.1.1]-propellane,
followed
coupling
vinyl-substituted
heterocycle,
which
represents
formal
decarboxylative
addition/double
bond
relay/protonation
sequence.
Journal of Chemical Education,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 27, 2025
Multicomponent
reactions
(MCRs)
are
fascinating
chemical
processes
where
three
or
more
starting
materials
come
together
to
form
a
single
product.
By
exploring
various
MCRs,
second-year
undergraduate
students
learn
about
the
synergy
between
different
functional
groups
and
how
they
influence
reactivity,
power
of
streamlined
approach
compared
conventional
stepwise
reactions,
critical
thinking
MCR
mechanisms.
Herein,
we
introduce
valuable
synthetic
method
for
constructing
heterocyclic
compounds
through
multiple-component
condensation/cycloaddition
process.
Specifically,
focus
on
1,4-dihydropyridine
(1,4-DHP),
privileged
N-heterocyclic
scaffold
widely
used
in
medicinal
chemistry,
particularly
4-aryl-3,5-dicarboxylated
derivatives.
The
experiment
provides
an
excellent
opportunity
explore
concept
green
chemistry
while
synthesizing
structurally
interesting
useful
molecules
using
readily
available
materials.
achieve
this
condensation
reaction
2-furaldehyde
(furfural),
acetoacetic
acid
tert-butyl
ester,
ammonium
acetate.
Key
features
teaching
include
following.
(1)
reaction:
involves
concise,
multicomponent
with
short
time.
(2)
Catalyst-free:
Notably,
proceeds
without
need
solvents
catalysts.
(3)
Visually
striking
system:
change
system
is
visually
evident,
enhancing
learning
experience.
(4)
Useful
methodology
drug
synthesis:
has
practical
implications
synthesis.
We
successfully
implemented
proposal
across
five
parallel
student
groups,
involving
approximately
150
participants.
experimental
procedures
encompass
organic
synthesis,
thin-layer
chromatography
(TLC),
nuclear
magnetic
resonance
(NMR)
analysis.
