Frontiers in Chemistry,
Год журнала:
2022,
Номер
10
Опубликована: Окт. 31, 2022
A
metal-
and
aldehyde-free
visible-light-driven
photoredox-neutral
alkene
acylarylation
with
readily
available
cyanoarenes
is
described.
variety
of
3-(arylmethyl)chroman-4-ones
(i.e.,
homoisoflavonoids)
analogs
are
efficiently
synthesized
good
functional
group
tolerance.
This
mild
protocol
relies
on
a
phosphoranyl
radical-mediated
acyl
radical-initiated
cyclization
selective
radical-radical
coupling
sequence,
also
further
highlighted
by
subsequent
derivatization
to
chromone
2H-chromene
as
well
its
application
in
the
three-component
acylarylation.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(31)
Опубликована: Июль 12, 2023
Abstract
A
visible
light‐induced
perfluoroalkylative
cyclization
of
3‐aza‐1,5‐dienes
leading
to
pentasubstituted
1,3‐dihydropyrrole‐2‐ones
is
presented.
The
reaction
regiospecific,
for
the
radical
adds
across
acrylamido
moiety,
whereas
enaminic
double
bond
functions
as
a
built‐in
trap.
It
could
be
carried
out
on
2‐gram
scale,
and
sunlight
usable
light
source.
Other
virtues
protocol
include
short
time,
low
catalyst
loading,
mild
conditions
broad
substrate
scope.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(24), С. 4513 - 4519
Опубликована: Окт. 31, 2023
Abstract
An
oxidant‐free
photocatalytic
[2+2+m]
cyclization
of
2‐cyanoaryl
acrylamides
with
2‐bromocarbonyls
is
reported,
enabling
the
assembly
biologically
important
N‐heterocycle‐fused
quinolinones
including
benzo[1,6]naphthyridinones
and
pyrrolo[3,2‐
c
]‐quinolines.
This
protocol
proceeds
through
a
radical
relay
pathway
alkene
difunctionalization
along
an
intramolecular
cyano
insertion
subsequent
site‐specific
functionalization
inert
C(
sp
3
)−H
bond
enabled
by
cyano‐derived
iminyl
radical‐mediated
1,n‐hydrogen
atom
transfer.
Notably,
this
transformation
selectively
formed
two
distinct
C−C
bonds,
one
C−N
bond,
quaternary
carbon
center
in
one‐pot
procedure.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(4), С. 2575 - 2582
Опубликована: Фев. 2, 2023
The
hitherto
difficult
site-selective
p-methoxybenzylation
of
secondary
amides
using
p-methoxybenzylated
alkylsilyl
peroxides
as
a
novel
agent
under
copper
catalysis
is
reported.
reaction
proceeds
mild
conditions
in
highly
chemoselective
manner.
This
approach
was
successfully
applied
to
the
peptides.
New Journal of Chemistry,
Год журнала:
2023,
Номер
47(26), С. 12487 - 12491
Опубликована: Янв. 1, 2023
A
facile
and
practical
silver-mediated
radical
cascade
cyclization
of
N
-allylamides
with
sodium
sulfinates
is
developed,
giving
a
series
sulfonated
oxazolines
in
moderate
to
good
yields.
Photocatalysis
is
becoming
increasingly
important
in
modern
chemistry
for
efficient
multicomponent
one-pot
synthesis.
However,
predicting
the
results
of
photocatalytic
reactions
using
artificial
intelligence
remains
challenging,
mostly
due
to
insufficient
number
and
incomplete
information
on
reaction
conditions
existing
databases.
In
this
study,
we
curated
Database
(PhotoCatDB),
which
consists
6,523
(of
6,175
are
multicomponent)
containing
condition
such
as
photocatalysts,
bases
or
acids,
additives,
solvents.
Before
adding
training
data,
attention-based
deep
learning
model
PhotoCat
pre-trained
USPTO
fine-tuned
PhotoCatDB
had
a
Top-1
accuracy
78.16%,
was
77.70%
higher
than
same
trained
only
database
14.53%
by
from
Reaxys.
After
further
increased
82.25%.
addition,
interpretability
reflected
its
attention
weights,
can
infer
model’s
understanding
chemistry.
Furthermore,
five
previously
unreported
predicted
were
successfully
validated
wet-lab
experiments,
demonstrating
potential
identifying
verifying
novel
photocatalysis
real-world
significance.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(20)
Опубликована: Фев. 28, 2024
Abstract
We
demonstrate
that
electrochemical‐induced
decarboxylation
enables
reliable
post‐polymerization
modification
and
degradation
of
polymers.
Polymers
containing
N
‐(acryloxy)phthalimides
were
subjected
to
electrochemical
under
mild
conditions,
which
led
the
formation
transient
alkyl
radicals.
By
installing
these
redox‐active
units,
we
systematically
modified
pendent
groups
chain
ends
polyacrylates.
This
approach
enabled
production
poly(ethylene‐
co
‐methyl
acrylate)
poly(propylene‐
copolymers,
are
difficult
synthesize
by
direct
polymerization.
Spectroscopic
chromatographic
techniques
reveal
transformations
near‐quantitative
on
several
polymer
systems.
Electrochemical
also
all‐methacrylate
poly(
‐(methacryloxy)phthalimide‐
methacrylate)
copolymers
with
a
efficiency
>95
%.
Chain
cleavage
is
achieved
through
‐hydroxyphthalimide
ester
subsequent
β‐scission
backbone
radical.
Electrochemistry
thus
shown
be
powerful
tool
in
selective
controlled
macromolecular
degradation.
Frontiers in Chemistry,
Год журнала:
2022,
Номер
10
Опубликована: Окт. 31, 2022
A
metal-
and
aldehyde-free
visible-light-driven
photoredox-neutral
alkene
acylarylation
with
readily
available
cyanoarenes
is
described.
variety
of
3-(arylmethyl)chroman-4-ones
(i.e.,
homoisoflavonoids)
analogs
are
efficiently
synthesized
good
functional
group
tolerance.
This
mild
protocol
relies
on
a
phosphoranyl
radical-mediated
acyl
radical-initiated
cyclization
selective
radical-radical
coupling
sequence,
also
further
highlighted
by
subsequent
derivatization
to
chromone
2H-chromene
as
well
its
application
in
the
three-component
acylarylation.
