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.
Chemical Science,
Год журнала:
2022,
Номер
13(48), С. 14213 - 14225
Опубликована: Янв. 1, 2022
This
Perspective
outlines
the
myriad
of
products
that
can
be
obtained
by
dearomatisation
and
functionalization
heteroarene
substrates.
Complex
3D
molecules
often
prepared
in
one
step
from
simple
arene
starting
materials.
Synthesis,
Год журнала:
2023,
Номер
56(01), С. 55 - 70
Опубликована: Янв. 17, 2023
Abstract
Despite
its
challenges,
the
skeletal
editing
of
mono-azaarenes
(pyridines,
quinolines,
and
isoquinolines)
has
shown
unparalleled
synthetic
utility
in
construction
complex
molecules
that
are
difficult
to
access
by
conventional
methods.
In
this
short
review,
we
summarize
three
most
recently
developed
strategies
for
deconstruction
azaarene
cores,
with
a
focus
on
their
generality,
limitations,
mechanistic
aspects.
Also,
application
strategy
total
synthesis
some
important
natural
products
is
discussed.
1
Introduction
2
Skeletal
Editing
Mono-Azaarenes
through
Zincke-like
Reactions
3
Mono-azaarenes
Aza-Buchner
4
via
Photoinduced
Radical
or
Energy-Transfer
Processes
5
Conclusion
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(41)
Опубликована: Май 28, 2024
Dearomative
construction
of
multiply-fused
2D/3D
frameworks,
composed
aromatic
two-dimensional
(2D)
rings
and
saturated
three-dimensional
(3D)
rings,
from
readily
available
quinolines
has
greatly
contributed
to
drug
discovery.
However,
dearomative
cycloadditions
in
the
presence
photocatalysts
usually
afford
5,6,7,8-tetrahydroquinoline
(THQ)-based
polycycles,
access
1,2,3,4-THQ-based
structures
remains
limited.
Herein,
we
present
a
chemo-,
regio-,
diastereo-,
enantioselective
transformation
into
6-6-4-membered
without
any
catalyst,
through
combination
nucleophilic
addition
borate-mediated
[2+2]
photocycloaddition.
Detailed
mechanistic
studies
revealed
that
photoexcited
borate
complex,
generated
quinoline,
organolithium,
HB(pin),
accelerates
cycloaddition
suppresses
rearomatization
occurs
conventional
Based
on
our
analysis,
also
developed
further
photoinduced
affording
other
types
frameworks
isoquinoline
phenanthrene.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(5), С. 3266 - 3276
Опубликована: Фев. 16, 2023
A
[3
+
2]
cycloaddition
reaction
of
N-aminopyridines,
N-aminoquinolines,
and
N-aminoisoquinolines
with
1-bromoethene-1-sulfonyl
fluoride
(BESF)
was
performed
to
obtain
optimum
yields
various
useful
pyrazolo[1,5-a]pyridinyl,
pyrazolo[1,5-a]quinolinyl,
pyrazolo[5,1-a]isoquinolinyl
sulfonyl
fluorides
(43–90%
yield).
The
transformation
process
showed
broad
substrate
specificity,
mild
conditions,
operational
simplicity.
Therefore,
the
has
great
applicable
value
in
field
medicinal
chemistry
other
disciplines.
Organic & Biomolecular Chemistry,
Год журнала:
2022,
Номер
20(34), С. 6923 - 6930
Опубликована: Янв. 1, 2022
An
effective
method
for
1,3,5-trisubstituted
pyrazoles
via
1,3-dipolar
cycloaddition
reaction
from
ninhydrin-derived
Morita–Baylis–Hillman
carbonates
and
nitrilimines
has
been
developed.
Organic Letters,
Год журнала:
2022,
Номер
24(16), С. 3048 - 3052
Опубликована: Апрель 15, 2022
Herein,
we
present
a
new
annulation
reaction
of
quinolinium
salts
with
indoles
and
paraformaldehyde,
which
enables
syn-diastereoselective
construction
vast
range
fused
tetrahydroquinolines
via
ruthenium-catalyzed
hydride-transfer-initiated
tandem
functionalization
the
quinoline
skeleton.
The
developed
transformation
proceeds
mild
conditions,
good
substrate
functional
group
compatibility,
readily
available
feedstocks,
operational
simplicity.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(6), С. 1388 - 1396
Опубликована: Янв. 23, 2024
Abstract
A
three‐component
phase‐transfer
catalytic
domino
reaction
involving
cyclohexane‐1,3‐dione‐derived
enaminones,
5‐alkenyl
rhodanines,
and
haloalkanes
has
been
developed.
This
protocol
produces
a
wide
range
of
3‐thioquinoline‐2,5‐diones
in
yields
52–81%.
The
construction
C−S
bond
at
the
C‐3
position
quinoline‐2,5‐dione
framework
expands
its
structural
diversity.
Studies
into
mechanism
revealed
that
undergoes
conjugate
addition,
ammonolysis,
elimination,
nucleophilic
substitution
sequence.
synthetic
potential
was
demonstrated
by
gram‐scale
syntheses
representative
products.
Chloroalkyl
chains
were
installed
on
sulfur
atoms
most
products
obtained
this
reaction.
Diversified
product
derivatives
exploiting
favorable
leaving
nature
chloride
moiety.
Organic Letters,
Год журнала:
2024,
Номер
26(10), С. 1996 - 2001
Опубликована: Март 4, 2024
Reductive
radical
dearomatization
N-alkyl
quinoline
quaternary
ammonium
salts
to
synthesize
structurally
complex
and
challenging
polysubstituted
benzo[d][1,3]oxazocines
was
first
reported.
The
mechanism
showed
various
allyl
alcohols
can
be
converted
into
alkyl
radicals
under
reduction
conditions
of
iron/silane.
These
then
nucleophilically
attack
the
C4
site
salts,
intramolecular
cyclization
resulting
intermediate
generates
target
product.
This
method
not
only
produced
a
series
novel
but
also
prepared
polycyclic
benzo[d][1,3]oxazocines.
Finally,
this
strategy
made
up
for
lack
reductive
reports
on
N-alkylquinolinium
had
advantages
mild
reaction
conditions,
wide
substrate
range,
product
structure.
Chemical Science,
Год журнала:
2023,
Номер
14(25), С. 6963 - 6969
Опубликована: Янв. 1, 2023
Simultaneous
dearomatizing
spirannulation
of
pyridinium
salts
is
still
in
its
infancy.
Here,
we
present
an
organized
skeletal
remodeling
designed
by
utilizing
interrupted
Corey-Chaykovsky
reaction
to
access
unprecedented
and
structurally
intriguing
molecular
architectures
such
as
the
vicinal
bis-spirocyclic
indanones
spirannulated
benzocycloheptanones.
This
hybrid
strategy
rationally
merges
nucleophilic
features
sulfur
ylides
with
electrophilic
achieve
regio-
stereoselective
synthesis
new
classes
cyclopropanoids.
The
plausible
mechanistic
pathways
were
derived
from
experimental
results
control
experiments.