Abstract
Compared
to
the
methods
that
rely
on
complex
and
structurally
unique
substrates
for
synthesis
of
heterocyclic
compounds
through
intra‐
intermolecular
cyclization,
strategies
starting
from
simple
readily
available
substrates,
combined
with
finely
tuned
catalytic
system
achieve
different
chemoselectivity,
offer
significant
advantages
in
terms
efficiency,
cost‐effectiveness,
versatility.
Herein,
we
present
a
palladium‐catalyzed
carbonylation
strategy
enables
selective
efficient
isoquinoline‐1,3(2
H
,4
)‐dione
indanone
derivatives
via
distinct
reaction
pathways.
Notably,
chemoselectivity
was
not
determined
by
differences
reactivity
at
sites
but
instead
arises
generation
active
palladium
species
under
nearly
identical
conditions,
which
subsequently
react
same
site
lead
products.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(45), С. 20875 - 20883
Опубликована: Окт. 31, 2022
We
report
the
first
palladium
hydride
enabled
hydroalkenylation
of
strained
molecules.
This
new
mild
protocol
proceeds
via
a
regio-
and
chemoselective
hydropalladation
step,
followed
by
photoinduced
radical
alkyl
Heck
reaction.
methodology
represents
reactivity
mode
for
molecules
opens
avenues
catalysis.
The
reaction
is
compatible
with
wide
range
functional
groups
can
be
applied
to
complex
structures,
delivering
diverse
array
highly
valuable
modifiable
alkenylated
cyclobutanes
cyclopropanes.
A
hydroalkenylation/diastereoselective
rearrangement
cascade
toward
cyclopentene
scaffold
has
also
been
demonstrated.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(5), С. 2794 - 2799
Опубликована: Янв. 25, 2023
A
photoexcited-nitroarene-mediated
anaerobic
C-H
hydroxylation
of
aliphatic
systems
is
reported.
The
success
this
reaction
due
to
the
bifunctional
nature
photoexcited
nitroarene,
which
serves
as
bond
activator
and
oxygen
atom
source.
Compared
previous
methods,
approach
cost-
atom-economical
commercial
availability
sole
mediator
reaction.
Because
conditions
transformation,
a
noteworthy
expansion
in
substrate
scope
can
be
obtained
compared
prior
reports.
Mechanistic
studies
support
that
nitroarenes
engage
successive
hydrogen
transfer
radical
recombination
events
with
hydrocarbons,
leading
N-arylhydroxylamine
ether
intermediates.
Spontaneous
fragmentation
these
intermediates
leads
key
products.
Chemical Reviews,
Год журнала:
2023,
Номер
123(22), С. 12313 - 12370
Опубликована: Ноя. 9, 2023
Late-stage
functionalization
(LSF)
introduces
functional
group
or
structural
modification
at
the
final
stage
of
synthesis
natural
products,
drugs,
and
complex
compounds.
It
is
anticipated
that
late-stage
would
improve
drug
discovery's
effectiveness
efficiency
hasten
creation
various
chemical
libraries.
Consequently,
products
a
productive
technique
to
produce
product
derivatives,
which
significantly
impacts
biology
development.
Carbon-carbon
bonds
make
up
fundamental
framework
organic
molecules.
Compared
with
carbon-carbon
bond
construction,
activation
can
directly
enable
molecular
editing
(deletion,
insertion,
atoms
groups
atoms)
provide
more
efficient
accurate
synthetic
strategy.
However,
selective
unstrained
still
one
most
challenging
projects
in
synthesis.
This
review
encompasses
strategies
employed
recent
years
for
cleavage
by
explicitly
focusing
on
their
applicability
functionalization.
expands
current
discourse
reactions
providing
comprehensive
overview
types
bonds.
includes
C-C(sp),
C-C(sp2),
C-C(sp3)
single
bonds;
double
triple
bonds,
focus
catalysis
transition
metals
organocatalysts.
Additionally,
specific
topics,
such
as
ring-opening
processes
involving
three-,
four-,
five-,
six-membered
rings,
are
discussed,
exemplar
applications
these
techniques
showcased
context
bioactive
molecules
discovery.
aims
shed
light
advancements
field
propose
potential
avenues
future
research
realm
Catalysts,
Год журнала:
2023,
Номер
13(2), С. 220 - 220
Опубликована: Янв. 18, 2023
Oxygen
atom
incorporation
into
organic
molecules
is
one
of
the
most
powerful
strategies
to
increase
their
pharmacological
activity
and
obtain
valuable
intermediates
in
synthesis.
Traditional
oxidizing
agents
perform
very
well,
but
environmental
impact
low
selectivity
constitute
significant
limitations.
On
contrary,
visible-light-promoted
oxygenations
represent
a
sustainable
method
for
compounds,
since
only
molecular
oxygen
photocatalyst
are
required.
Therefore,
photocatalytic
oxygenation
reactions
exhibit
high
atom-economy
eco-compatibility.
This
mini-review
collects
analyzes
recent
literature
on
organo-photocatalysis
applications
promote
selective
substrates.
In
particular,
acridinium
salts,
Eosin
Y,
Rose
Bengal,
cyano-arenes,
flavinium
quinone-based
dyes
widely
used
as
photocatalysts
several
transformations
alkanes,
alkenes,
alkynes,
aromatic
amines,
phosphines,
silanes,
thioethers.
this
context,
organo-photocatalysts
proved
be
highly
efficient
catalytic
terms,
showing
similar
or
even
superior
performances
with
respect
metal-based
counterparts,
while
maintaining
impact.
addition,
given
mild
reaction
conditions,
photo-oxygenation
processes
often
display
remarkable
selectivity,
which
striking
feature
late-stage
functionalization
complex
molecules.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(14), С. 9499 - 9505
Опубликована: Март 24, 2024
Herein,
we
report
that
readily
accessible
azoxy-triazenes
can
serve
as
nitrogen
atom
sources
under
visible
light
excitation
for
the
phthalimido-protected
aziridination
of
alkenes.
This
approach
eliminates
need
external
oxidants,
precious
transition
metals,
and
photocatalysts,
marking
a
departure
from
conventional
methods.
The
versatility
this
transformation
extends
to
selective
both
activated
unactivated
multisubstituted
alkenes
varying
electronic
profiles.
Notably,
process
avoids
formation
competing
C–H
insertion
products.
described
protocol
is
operationally
simple,
scalable,
adaptable
photoflow
conditions.
Mechanistic
studies
support
idea
photofragmentation
results
in
generation
free
singlet
nitrene.
Furthermore,
mild
photoredox-catalyzed
N–N
cleavage
protecting
group
furnish
aziridines
reported.
Our
findings
contribute
advancement
sustainable
practical
methodologies
synthesis
nitrogen-containing
compounds,
showcasing
potential
broader
applications
synthetic
chemistry.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(10), С. 4926 - 4975
Опубликована: Янв. 1, 2024
In
search
for
the
perfect
wave(length).
This
review
is
dedicated
to
recent
efforts
in
development
of
visible
light
driven
photochemical
strategies
occurring
coloured
organic
compounds.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Май 31, 2024
Abstract
Controllable
photofluorochromic
systems
with
high
contrast
and
multicolor
in
both
solutions
solid
states
are
ideal
candidates
for
the
development
of
dynamic
artificial
intelligence.
However,
it
is
still
challenging
to
realize
multiple
photochromism
within
one
single
molecule,
not
mention
good
controllability.
Herein,
we
report
an
aggregation-induced
emission
luminogen
TPE-2MO2NT
that
undergoes
oxidation
cleavage
upon
light
irradiation
accompanied
by
tunable
from
orange
blue
time-dependence.
The
photocleavage
mechanism
revealed
self-generation
reactive
oxidants
driving
catalyst-free
oxidative
process.
A
comprehensive
analysis
other
comparative
molecules
demonstrates
molecular
scaffold
can
be
easily
modified
extended.
Further,
microenvironmental
controllability
photoreaction
polymer
matrices
enables
fabrication
fluorescence
images
4D
information
codes,
providing
strategies
advanced
controllable
encryption.
