Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(15), P. 2657 - 2662
Published: April 11, 2023
An
N-heterocyclic
carbene
(NHC)-catalyzed
facile
assembly
of
α-sulfonyl
ketones
has
been
successfully
developed
through
a
radical-mediated
sulfonyl
methylation
readily
available
aldehydes.
This
protocol
involves
the
effective
single-electron
transfer
reduction
α-iodosulfones
by
NHC-bound
Breslow
intermediates,
thus
allowing
subsequent
radical-radical
coupling
to
afford
target
compounds.
Moreover,
catalytic
system
was
found
be
equally
for
difunctionalization
styrenes
and
1,3-enynes
via
three-component
radical
relay
process.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(8), P. 4237 - 4352
Published: Jan. 24, 2023
The
emergence
of
modern
photocatalysis,
characterized
by
mildness
and
selectivity,
has
significantly
spurred
innovative
late-stage
C–H
functionalization
approaches
that
make
use
low
energy
photons
as
a
controllable
source.
Compared
to
traditional
strategies,
photocatalysis
paves
the
way
toward
complementary
and/or
previously
unattainable
regio-
chemoselectivities.
Merging
compelling
benefits
with
workflow
offers
potentially
unmatched
arsenal
tackle
drug
development
campaigns
beyond.
This
Review
highlights
photocatalytic
strategies
small-molecule
drugs,
agrochemicals,
natural
products,
classified
according
targeted
bond
newly
formed
one.
Emphasis
is
devoted
identifying,
describing,
comparing
main
mechanistic
scenarios.
draws
critical
comparison
between
established
ionic
chemistry
photocatalyzed
radical-based
manifolds.
aims
establish
current
state-of-the-art
illustrate
key
unsolved
challenges
be
addressed
in
future.
authors
aim
introduce
general
readership
functionalization,
specialist
practitioners
evaluation
methodologies,
potential
for
improvement,
future
uncharted
directions.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(16), P. 4230 - 4247
Published: Jan. 1, 2023
This
review
explores
the
benefits
of
flow
chemistry
and
dispels
notion
that
it
is
a
mysterious
“black
box”,
demonstrating
how
can
push
boundaries
organic
synthesis
through
understanding
its
governing
principles.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(5), P. 3013 - 3032
Published: Feb. 18, 2022
Sulfones
are
common,
readily
available
reagents
that
have
recently
attracted
attention
as
versatile
for
cross-coupling
reactions.
This
Review
summarizes
advances
in
desulfonylative
transformations
of
sulfones
affected
by
molecular
catalysis,
including
transition-metal
catalysts,
photocatalysts,
and
organocatalysts.
In
addition
to
catalyst
choice,
the
design
sulfonyl
group
is
a
critical
factor
control
reactivity.
The
concepts
presented
herein
will
provide
new
strategies
construct
diverse
molecules
with
high
efficiency
modularity.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(15), P. 6774 - 6823
Published: Jan. 1, 2022
Sulfones
are
excellent
candidates
for
the
design
of
new
C–C
and
C–X
bond-forming
reactions
owing
to
easy
activation
C–S
bonds.
This
review
focuses
on
challenges
recent
opportunities
catalytic
functionalization
sulfones.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(11), P. 3169 - 3175
Published: Jan. 1, 2022
The
modulation
of
selectivity
highly
reactive
carbon
radical
cross-coupling
for
the
construction
C-C
bonds
represents
a
challenging
task
in
organic
chemistry.
N-Heterocyclic
carbene
(NHC)
catalyzed
transformations
have
opened
new
avenue
acyl
With
this
method,
selective
an
with
alkyl
efficient
was
successfully
realized.
However,
reaction
radicals
vinyl
has
been
much
less
investigated.
We
herein
describe
NHC
and
visible
light-mediated
photoredox
co-catalyzed
1,4-sulfonylacylation
1,3-enynes,
providing
structurally
diversified
valuable
tetrasubstituted
allenyl
ketones.
Mechanistic
studies
indicated
that
ketyl
are
formed
from
aroyl
fluorides
via
oxidative
quenching
photocatalyst
excited
state,
generated
chemo-specific
sulfonyl
addition
to
finally,
key
provides
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Feb. 17, 2024
Abstract
Transition
metal-catalyzed
reductive
difunctionalization
of
alkenes
with
alkyl
halides
is
a
powerful
method
for
upgrading
commodity
chemicals
into
densely
functionalized
molecules.
However,
super
stoichiometric
amounts
metal
reductant
and
the
requirement
installing
directing
group
to
suppress
inherent
β-H
elimination
bring
great
limitations
this
type
reaction.
We
demonstrate
herein
that
two
different
accessible
via
radical-anion
relay
Na
2
S
O
4
as
both
sulfone-source.
The
together
electron-shuttle
catalyst
crucial
divert
mechanistic
pathway
toward
formation
sulfone
anion
instead
previously
reported
alkylmetal
intermediates.
Mechanistic
studies
allow
identification
carbon-centered
radical
sulfur-centered
radical,
which
are
in
equilibrium
capture
or
extrusion
SO
could
be
converted
accelerated
by
iron
catalysis,
leading
observed
high
chemoselectivity.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 3, 2025
A
Ru-catalyzed
defluorinative
cyclization
of
polyfluoroalkyl
tetralones
has
been
developed
under
visible-light
irradiation
for
the
precise
assembly
γ-pyrones
featuring
α-perfluoroalkyl
and
β-fluorine
substituents.
Selective
functionalization
five
C(sp3)–F
bonds
at
three
carbon
sites
on
perfluoroalkyl
chain
provides
a
new
mode
utilizing
polyfluorides
as
versatile
synthons
to
access
difficult-to-obtain
heterocyclic
scaffolds.
Moreover,
sulfinate
salt
serves
dual
roles
an
oxygen
source
creating
carbonyl
group
defluorinating
promoter.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(13), P. 2474 - 2478
Published: March 9, 2022
Sulfonyl
fluorides
are
useful
building
blocks
in
a
wide
array
of
fields.
Herein,
we
report
catalytic
decarboxylative
fluorosulfonylation
approach
for
converting
abundant
aliphatic
carboxylic
acids
to
the
corresponding
sulfonyl
fluorides.
This
transformation
is
enabled
by
simple
preactivation
as
aldoxime
esters
and
energy-transfer-mediated
photocatalysis.
operationally
method
proceeds
with
high
functional-group
tolerance
under
mild
redox-neutral
conditions.
Organic Chemistry Frontiers,
Journal Year:
2022,
Volume and Issue:
9(4), P. 917 - 922
Published: Jan. 1, 2022
The
synthesis
of
β-azidosulfones
starting
from
alkenes,
cycloketone
oxime
esters,
trimethylsilyl
azide
and
a
sulfur
dioxide
surrogate
DABCO·(SO
2
)
under
iron
catalysis
is
developed.
