Abstract
Direct
functionalization
of
C−H
bonds
is
the
most
expeditious
strategy
to
build
complexity
into
organic
molecules.
Unfortunately,
Pd‐catalyzed
arylation
strategies
require
high
temperatures
and/or
stoichiometric
oxidants.
The
discovery
metallaphotoredox
in
2011
forged
a
new
approach
achieve
metal
catalyzed
at
room
temperature.
Since
this
discovery,
reports
still
use
explosive
diazonium
salts
as
aryl
radical
precursors.
Alternatively,
single
report
uses
bench‐stable
diaryliodonium
salts,
albeit
with
an
Ir‐based
photocatalyst.
In
study,
we
develop
organophotoredox
manifold
that
enables
numerous
N
‐aryl
amide
substrates.
results
present
are
expected
revitalize
temperature
arylations
wide‐ranging
classes
bonds.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(12), С. 1399 - 1406
Опубликована: Фев. 29, 2024
Comprehensive
Summary
A
general
and
convenient
photoredox‐catalyzed
acylation
alkylcyanation
of
MBH
acetates
has
been
established,
enabling
the
assembly
C(sp
2
)–C(sp
3
)
bond
by
a
nitrogen‐centered
radical
strategy
for
synthesis
trisubstituted
alkenes
in
moderate
to
excellent
chemical
yields
(48
examples
total).
The
reaction
with
acyl
(indanone)
oxime
esters
afforded
containing
1,4‐dicarbonyl
groups.
Interestingly,
use
Eosin
Y
as
photocatalyst
catalytic
system
resulted
formation
distal
cyano
group‐anchored
via
deconstructive
functionalization
cycloketone
esters.
Notably,
these
resulting
compounds
could
be
applied
late‐stage
transformations,
providing
important
methods
dihydropyridazin‐3(2
H
)‐one.
Organic Letters,
Год журнала:
2024,
Номер
26(15), С. 3189 - 3194
Опубликована: Апрель 8, 2024
A
new
umpolung
approach
to
the
C3–H
functionalization
of
indoles
with
diverse
nucleophiles
based
on
intermediate
formation
I(III)
reagents
is
described.
The
3,5-dimethylisoxazol-4-yl
auxiliary
allows
for
selective
indole
transfer
under
catalyst-free
conditions,
which
was
impossible
using
previously
reported
reagents.
Combining
mildness
transition-metal-free
conditions
and
high
reactivity
hypervalent
iodine
reagents,
this
protocol
tolerates
various
functional
groups
provides
access
that
are
difficult
prepare
conventionally.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(7), С. 4877 - 4887
Опубликована: Март 8, 2024
General
and
convenient
visible-light-promoted
alkylsulfonylation
cyanoalkylsulfonylation
of
MBH
adducts
have
been
developed
through
the
multicomponent
insertion
sulfur
dioxide,
enabling
assembly
two
C–S
bonds
to
generate
structurally
diverse
allylic
alkylsulfones
(43
examples
in
total).
The
reaction
with
potassium
alkyltrifluoroborates
1,4-diazabicyclo[2.2.2]octane
bis(sulfur
dioxide)
adduct
afforded
sulfones
generally
good
yields.
Notably,
addition
N,N,N′,N′-tetramethylethylenediamine
as
a
base
into
photocatalytic
system
led
yielding
an
alkyl
sulfonyl
unit
cyano
group-anchored
trisubstituted
alkenes
by
utilizing
cycloketone
oxime
esters
C-radical
precursors.
Both
these
reactions
constructed
bonds,
all
desired
products
were
obtained
moderate
excellent
yields
complete
stereospecificity.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(9), С. 2063 - 2071
Опубликована: Фев. 29, 2024
Abstract
Herein,
we
demonstrate
that
carbamoyl
radicals
generated
through
an
organophotocatalytic
protocol
from
4‐carbamoyl‐dihydropyridines
(carbamoyl‐DHPs)
can
be
incorporated
into
Morita‐Baylis‐Hillman
(MBH)
carbonates,
affording
a
range
of
polyfunctionalized
scaffolds
with
yields
ranging
63–98%.
Reaction
monitoring
experiments,
scale‐up,
reuse
the
organophotocatalyst,
and
hydrogenation
succinamic
ester's
alkene
moiety
was
also
conducted,
in
order
to
showcase
mechanistic
features
robustness
this
photochemical
protocol.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(14), С. 9923 - 9928
Опубликована: Июль 1, 2024
Diethyl
acetamidomalonate
(DEAM)
has
been
widely
used
for
the
synthesis
of
α-amino
acids
via
C-alkylation
under
basic
conditions
followed
by
hydrolysis/decarboxylation.
In
contrast,
C-arylation
this
reagent
remains
undeveloped.
Herein,
we
report
a
novel
strategy
racemic
α-arylglycines
based
on
selective
arylation
DEAM
with
diaryliodonium
salts
mild,
transition
metal-free
conditions.
The
reaction
features
good
functional
group
tolerance
and
easy
scalability
is
applicable
to
chemoselective
C-H-modification
arenes
including
approved
drugs,
thus
enabling
straightforward
approach
complex
that
would
be
challenging
make
otherwise.
Organic Letters,
Год журнала:
2024,
Номер
26(37), С. 7864 - 7868
Опубликована: Сен. 9, 2024
A
hypervalent
iodine-reagent-based
C-H
functionalization
strategy
was
utilized
to
synthesize
diaryl
ethers.
This
method
directly
transforms
various
arenes
into
their
corresponding
diaryliodonium
salts,
followed
by
a
C-O
coupling
reaction
produce
structurally
diverse
The
efficacy
of
this
approach
in
the
late-stage
structural
modifications
complex
molecules
demonstrated.
Sulfone
motifs
play
important
roles
in
bioactive
compounds
and
functional
materials.
The
development
of
efficient
methodologies
for
constructing
sulfonyl-containing
has
thus
attracted
considerable
attention.
Here,
we
introduce
a
protocol
the
preparation
alkyl
aryl
sulfones
under
mild
conditions.
This
employs
β-thioamide
sulfone
as
novel
motif
donor.
It
forms
sulfinates
situ
basic
conditions,
which
then
undergo
cross-coupling
with
intermediates
that
were
generated
from
ligand-free
copper-catalyzed
cyclopropenes
(CPEs)
ring
opening.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 10, 2025
A
palladium-catalyzed
decarboxylative
allylic
sulfonylation
reaction
of
vinyloxazolidine-2,4-diones
with
inexpensive
and
readily
available
sodium
sulfinates
as
reagents
has
been
developed.
Under
the
catalysis
Pd(PPh3)4,
a
wide
range
γ-sulfonyl-α,β-unsaturated
amides
can
be
synthesized
in
good
to
excellent
yields.
The
developed
protocol
is
characterized
by
exclusive
regioselectivity,
mild
conditions,
broad
substrate
scope,
functional
group
tolerance,
suitable
for
gram-scale
synthesis.
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
transition-metal-free
protocol
for
the
unsymmetrical
radical
1,3-difunctionalization
of
alkenes
has
been
established
first
time
in
form
1,3-difluoroalkylcarboxylation
by
a
photocatalytic
three-component
reaction
allyl
formates,
trifluoroacetanilides,
and
cesium
formate.
This
employs
formate
as
carboxylating
reagent
trifluoroacetanilide
difluoroalkylating
via
C-F
bond
activation.
As
result,
series
previously
inaccessible
difluorinated
adipic
acid
derivatives
can
be
easily
efficient
prepared.
Mechanism
studies
reveal
that
triple
kinetic-controlled
self-ordering
is
key
to
this
unique
reaction.
sorting
involves
fast
initiation
CO2
anion
its
chemoselective
addition
reduction,
followed
slow
generation
fluoroalkyl
chemo-/regioselective
addition.
Notably,
strategy
also
suitable
cyclic
through
diastereoselectively
constructing
two
or
three
consecutive
stereocenters.
