Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июль 19, 2024
Abstract
Visible-light
photocatalysis
has
evolved
as
a
powerful
technique
to
enable
controllable
radical
reactions.
Exploring
unique
photocatalytic
mode
for
obtaining
new
chemoselectivity
and
product
diversity
is
of
great
significance.
Herein,
we
present
photo-induced
chemoselective
1,2-diheteroarylation
unactivated
alkenes
utilizing
halopyridines
quinolines.
The
ring-fused
azaarenes
serve
not
only
substrate,
but
also
potential
precursors
halogen-atom
abstraction
pyridyl
generation
in
this
photocatalysis.
As
complement
metal
catalysis,
process
with
mild
redox
neutral
conditions
assembles
two
different
heteroaryl
groups
into
regioselectively
contribute
broad
substrates
scope.
obtained
products
containing
aza-arene
units
permit
various
further
diversifications,
demonstrating
the
synthetic
utility
protocol.
We
anticipate
that
protocol
will
trigger
advancement
alkyl/aryl
halides
activation.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(3), С. 1068 - 1089
Опубликована: Янв. 1, 2024
Leveraging
light
energy
to
expose
the
‘dark’
reactive
states
describes
whole
essence
of
triplet–triplet
transfer.
This
offers
an
impressive
opportunity
conduct
a
multitude
diverse
reactions
and
access
sought-after
molecular
motifs.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(22), С. 12324 - 12332
Опубликована: Май 26, 2023
Dearomative
photocycloadditions
are
valuable
chemical
transformations,
serving
as
an
efficient
platform
to
create
three-dimensional
molecular
complexity.
However,
the
photolability
of
original
addition
product
especially
within
context
ortho
cycloadditions
often
causes
undesired
consecutive
rearrangements,
rendering
these
cycloadducts
elusive.
Herein,
we
report
ortho-selective
intermolecular
photocycloaddition
bicyclic
aza-arenes
including
(iso)quinolines,
quinazolines,
and
quinoxalines
by
utilizing
a
strain-release
approach.
With
bicyclo[1.1.0]butanes
coupling
partners,
this
dearomative
[2π
+
2σ]
cycloaddition
enables
straightforward
construction
C(sp3)-rich
bicyclo[2.1.1]hexanes
directly
connected
N-heteroarenes.
Photophysical
experiments
DFT
calculations
revealed
origin
selectivity
indicate
that,
in
originally
proposed
energy
transfer
or
direct
excitation
pathways,
chain
reaction
mechanism
is
operative
depending
on
conditions.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(4), С. 2789 - 2797
Опубликована: Янв. 18, 2024
Dearomative
photocycloaddition
of
monocyclic
arenes
is
an
appealing
strategy
for
comprehending
the
concept
"escape
from
flatland".
This
brings
replacement
readily
available
planar
aromatic
hydrocarbon
units
with
a
3D
fused
bicyclic
core
sp3-enriched
carbon
units.
Herein,
we
outline
intermolecular
approach
dearomative
phenols.
In
order
to
circumvent
ground-state
aromaticity
and
construct
conformationally
restrained
building
blocks,
bicyclo[1.1.0]butanes
were
chosen
as
coupling
partners.
renders
straightforward
access
bicyclo[2.1.1]hexane
unit
cyclic
enone
moiety,
which
further
contributed
synthetic
linchpin
postmodifications.
Mechanistic
experiment
advocates
plausible
onset
both
reactants,
depending
on
redox
potential.
Chemical Reviews,
Год журнала:
2024,
Номер
124(3), С. 1122 - 1246
Опубликована: Янв. 2, 2024
Dearomatization
reactions
have
become
fundamental
chemical
transformations
in
organic
synthesis
since
they
allow
for
the
generation
of
three-dimensional
complexity
from
two-dimensional
precursors,
bridging
arene
feedstocks
with
alicyclic
structures.
When
those
processes
are
applied
to
pyridines,
quinolines,
and
isoquinolines,
partially
or
fully
saturated
nitrogen
heterocycles
formed,
which
among
most
significant
structural
components
pharmaceuticals
natural
products.
The
inherent
challenge
lies
low
reactivity
heteroaromatic
substrates,
makes
dearomatization
process
thermodynamically
unfavorable.
Usually,
connecting
event
irreversible
formation
a
strong
C–C,
C–H,
C–heteroatom
bond
compensates
energy
required
disrupt
aromaticity.
This
aromaticity
breakup
normally
results
1,2-
1,4-functionalization
heterocycle.
Moreover,
combination
these
subsequent
tandem
stepwise
protocols
allows
multiple
heterocycle
functionalizations,
giving
access
complex
molecular
skeletons.
aim
this
review,
covers
period
2016
2022,
is
update
state
art
nucleophilic
dearomatizations
showing
extraordinary
ability
dearomative
methodology
indicating
their
limitations
future
trends.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(12)
Опубликована: Дек. 5, 2023
London
dispersion
(LD)
interactions
are
the
main
contribution
of
attractive
part
van
der
Waals
potential.
Even
though
LD
effects
driving
force
for
molecular
aggregation
and
recognition,
role
these
omnipresent
in
structure
reactivity
had
been
largely
underappreciated
over
decades.
However,
recent
years
considerable
efforts
have
made
to
thoroughly
study
their
potential
as
a
chemical
design
element
structures
catalysis.
This
was
possible
through
fruitful
interplay
theory
experiment.
review
highlights
results
advances
utilizing
structural
motif
understand
utilize
intra-
intermolecularly
LD-stabilized
systems.
Additionally,
we
focus
on
quantification
fundamental
reactions.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(32)
Опубликована: Июль 3, 2023
Abstract
The
synthesis
of
polycyclic
compounds
is
high
interest
due
to
the
prevalence
these
motifs
in
drugs
and
natural
products.
Herein,
we
report
on
stereoselective
construction
3D
bicyclic
scaffolds
azetidine
derivatives
by
modulation
N
‐sulfonylimines
achieve
either
[4+2]‐
or
[2+2]‐cycloaddition
reactions.
utility
method
was
established
further
product.
Mechanistic
studies
are
also
included,
which
support
reaction
via
Dexter
energy
transfer.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(12), С. 6600 - 6624
Опубликована: Янв. 1, 2024
Dearomatization
has
emerged
as
a
powerful
tool
for
rapid
construction
of
3D
molecular
architectures
from
simple,
abundant,
and
planar
(hetero)arenes.
The
field
evolved
beyond
simple
dearomatization
driven
by
new
synthetic
technology
development.
With
the
renaissance
photocatalysis
expansion
activation
mode,
last
few
years
have
witnessed
impressive
developments
in
innovative
photochemical
methodologies,
enabling
skeletal
modifications
dearomatized
structures.
They
offer
truly
efficient
useful
tools
facile
highly
complex
structures,
which
are
viable
natural
product
synthesis
drug
discovery.
In
this
review,
we
aim
to
provide
mechanistically
insightful
overview
on
these
innovations
based
degree
alteration,
categorized
into
dearomative
functionalization
editing,
highlight
their
utilities.
