Organophosphorus
aza-heterocycles
are
widely
found
in
the
framework
of
bioactive
molecules,
materials,
and
commercially
available
medications.
We
report
a
photoredox-catalyzed
cascade
radical
addition/annulation
sequences
acyclic
phosphinimides
with
organohalides
under
mild
external
oxidant-free
reaction
conditions.
A
wide
range
functionalized
bearing
quaternary
carbon
center
can
be
efficiently
selectively
produced
by
employing
diverse
precursors,
which
including
sulfonyl,
perfluoroalkyl,
trichloromethyl,
carbonyl
halides,
respectively.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(9), P. 6117 - 6125
Published: April 24, 2024
The
first
paired
electrolysis-enabled
arylation
of
quinoxalin-2(1H)-ones
was
achieved
using
cyanoarenes
as
the
reagents.
A
variety
3-arylquinoxalin-2(1H)-ones
with
various
important
functional
groups
were
obtained
in
moderate
to
good
yields
under
metal-
and
chemical
oxidant-free
conditions.
With
a
pair
reductive
oxidative
processes
occurring
among
substrates
reaction
intermediates,
power
consumption
can
be
dramatically
reduced.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(22), P. 4727 - 4732
Published: May 29, 2024
A
visible-light-induced
photocatalyst-free
acylative
pyridylation
of
styrenes
with
4-acyl-1,4-dihydropyridines
(DHPs)
and
4-cyanopyridines
has
been
described,
featuring
mild
reaction
conditions,
a
broad
substrate
scope,
good
functional
group
tolerance.
The
could
also
be
performed
under
sunlight
irradiation
albeit
slightly
lower
conversion.
4-Acyl-1,4-DHPs
serve
dual
role,
acting
as
both
photoreductant
to
reduce
the
cyanopyridine
its
radical
anion
intermediate
precursor
produce
acyl
radical.
mechanism
was
especially
elucidated
through
Hammett
analysis,
quadratic
linear
regression
analysis
by
using
parameters,
σmb
σjj·.
findings
from
further
demonstrate
that
rate-limiting
step
process
is
single
electron
transfer
between
4-acyl-1,4-DHPs
4-cyanopyridines.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(33), P. 4451 - 4454
Published: Jan. 1, 2024
Photocatalytic
α-C(sp
3
)–H
pyridination
of
N
-arylglycine
derivatives
and
-arylamines
with
cyanopyridines
was
developed
through
radical–radical
cross-coupling
under
redox-neutral
conditions.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(31)
Published: April 3, 2024
Abstract
Saturated
heterocycles
are
important
class
of
structural
scaffolds
in
small‐molecule
drugs,
natural
products,
and
synthetic
intermediates.
Here,
we
disclosed
a
metal
free,
mild,
scalable
functionalization
saturated
using
vinylarenes
as
linchpin
approach.
Key
to
success
this
transformation
is
the
employing
simple
cheap
benzophenone
hydrogen
atom
transfer
(HAT)
catalyst.
This
operationally
robust
process
was
used
for
making
diverse
functionalized
heterocycles.
Furthermore,
aldehydes,
alkane,
alcohol
have
been
under
optimized
conditions.
The
potential
pharmaceutical
utility
procedure
has
also
demonstrated
by
late‐stage
bioactive
compounds
molecules.
Initial
mechanism
studies
control
experiments
were
performed
elucidate
reactions
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(25), P. 5323 - 5328
Published: June 17, 2024
Amino
acids
and
aromatic
nitrogen
heterocycles
are
widely
used
in
pharmaceuticals.
Herein,
we
present
an
effective
visible-light-driven
thiobenzoic
acid
(TBA)-catalyzed
decyanative
C(sp3)–H
heteroarylation
of
glycine
derivatives.
This
process
occurs
under
mild
straightforward
conditions,
affording
a
range
valuable
yet
challenging-to-obtain
α-heteroaryl
amino
Moreover,
this
organocatalytic
C(sp3)–C(sp2)
bond
formation
reaction
is
applicable
to
the
late-stage
modification
various
short
peptides.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(14), P. 3138 - 3143
Published: May 11, 2024
Abstract
Visible‐light‐induced
difunctionalization
of
alkenes
is
a
powerful
strategy
for
constructing
complex
molecules.
Herein,
we
disclose
three‐component
1,2‐alkylpyridylation
under
mild
and
photosensitizers‐free
conditions.
UV‐vis
absorption
spectroscopy
studies
NMR
titration
experiments
indicate
that
the
formation
an
EDA
between
4‐alkyl‐DHPs
4‐cyanopyridines.
Primary,
secondary,
tertiary
C(
sp
3
)‐centered
radicals
were
formed
by
homolytic
cleavage
4‐alkyl‐DHPs.
Gram‐scale
synthesis
late‐stage
functionalization
medicinally
relevant
molecules
showed
synthetic
potential
our
methodology.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 7, 2025
Reported
herein
is
a
concise
synthesis
of
sulfoximidoyl
amidines
enabled
by
Pd-catalyzed
cascade
aza-Claisen
rearrangement
and
nucleophilic
reaction
at
room
temperature.
Free
NH-sulfoximines
N-allylynamides
were
employed
as
the
modular
building
blocks
to
produce
expected
sulfoximine
amidine
derivatives
in
highly
chemoselective
models
100%
atom
efficiency.
A
broad
range
functional
groups
well
tolerated
under
these
gentle
conditions
give
desired
products
generally
good
excellent
yields.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 7, 2025
The
β-pyridyl
amide
is
a
critical
scaffold
in
medical
discovery
yet
lacks
efficient
synthetic
methods.
Here,
we
describe,
for
the
first
time,
visible-light-induced,
redox-neutral
radical
cross-coupling
reaction
involving
alkenes,
oxamic
acids,
and
cyanopyridines
that
offers
versatile
assembly
of
β-pyridylamides.
This
approach
features
mild
conditions,
high
step
efficiency,
substrate
breadth,
providing
green
strategy
alkene
pyridyl-carbamoylation.
Achieving
this
transformation
relies
on
catalytic
system,
which
adeptly
avoids
competing
nucleophilic
carbamoyl
with
electrophilic
pyridyl
radical,
enabling
three-component
tandem
process
chemoselectivity.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 27, 2025
The
activation
of
Csp2–I
bonds
in
iodobenzenes
and
their
derivatives
is
a
highly
valuable
research
topic.
Most
known
methods
predominantly
rely
on
transition
metal
catalysis,
which
often
necessitates
the
use
oxidants,
additives,
ligands,
harsh
reaction
conditions.
Photocatalysis
has
emerged
last
decades
as
an
excellent
alternative
to
drive
intriguing
organic
transformations
via
various
chemical
bond
cleavages,
while
photocontrolled
direct
cleavage
O-tethered
iodoarenes
rare
due
its
high
reduction
potential.
To
address
this
challenge,
we
have
provided
relay
reductive
photocatalysis
strategy
amplify
function
low
potential
photocatalysts
using
cyanoalkenes
photoredox
mediators
achieve
iodoarenes.
Moreover,
it
noteworthy
that
cyanoarenes
are
simultaneously
involved
coupling
reagents
radical
cyclization/coupling
process
between
form
benzo-fused
oxygen-containing
heterocyclic
compounds
with
different
scaffolds.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 2, 2025
In
this
work,
a
photocatalytic
redox-neutral
carbon-carbon
bond
metathesis
and
transalkylation
of
heteroarenes
was
established.
When
CBZ6
used
as
the
photocatalyst,
alkyl
migration
from
2-alkyl
pyrrolidines
or
piperidines
to
heteroaryl
nitriles
occurred,
affording
heteroaryl-substituted
tertiary
ethers
in
up
98%
yields.
The
cyanyl
groups
released
nitrites
are
trapped
by
donors
form
2-cyano
piperidines.
These
can
be
recycled
for
regeneration
donors.
A
wide
range
substrates
has
been
proven
suitable.
Preliminary
mechanistic
investigations
revealed
nature
reaction.
