Abstract
DABCO
promoted
one‐pot
three‐component
reaction
of
aromatic
amines,
dialkyl
but‐2‐ynedioates
and
MBH
nitriles
isatins
selectively
afforded
two
diastereomeric
spiro[indoline‐3,4′‐pyridines]
in
comparable
yields.
On
the
other
hand,
cyclization
carbonates
DCM
at
room
temperature
gave
spiro[cyclopentane‐1,3′‐indoline]
derivatives,
while
chloroform
70
°C
resulted
unique
cyclopenta[
c
]quinolone
derivatives
with
ring‐opening
isatin
moiety.
A
plausible
mechanism
was
rationally
proposed
to
explain
formation
different
products.
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.
Chemistry - A European Journal,
Год журнала:
2020,
Номер
27(13), С. 4216 - 4229
Опубликована: Авг. 26, 2020
Abstract
Organic
superbases
are
a
distinct
and
increasingly
utilized
class
of
Brønsted
base
that
possess
properties
complementary
to
common
inorganic
bases.
This
Concept
article
discusses
recent
applications
commercial
organic
in
modern
synthetic
methodologies.
Examples
the
advantages
three
areas
highlighted,
including
discovery
new
base‐catalyzed
reactions,
optimization
reactions
require
stoichiometric
base,
high‐throughput
experimentation
technology.
Organic & Biomolecular Chemistry,
Год журнала:
2021,
Номер
19(18), С. 3960 - 3982
Опубликована: Янв. 1, 2021
Bridged
polycycles
are
privileged
molecular
skeletons
with
wide
occurrence
in
bioactive
natural
products
and
pharmaceuticals.
Therefore,
they
have
been
the
pursing
target
molecules
of
numerous
chemists.
The
rapid
convenient
generation
sp3-rich
complex
three-dimensional
from
simple
easily
available
aromatics
has
made
dearomatization
a
highly
valuable
synthetic
tool
for
construction
rigid
challenging
bridged
rings.
This
review
summarizes
the-state-of-the-art
advances
strategies
application
ring
formation,
discusses
their
advantages
limitations
in-depth
mechanism,
highlights
value
total
synthesis
products.
We
wish
this
will
provide
an
important
reference
medicinal
chemists
inspire
further
development
intriguing
research
area.
Organic Letters,
Год журнала:
2022,
Номер
24(10), С. 2008 - 2013
Опубликована: Март 10, 2022
We
report
an
unexpected
dearomative
periphery
modification
strategy
for
transforming
quinolinium
salts
into
structurally
crowded
pyrrolidine–tetrahydroquinoline
polycyclic
systems
with
complete
regio-
and
diastereoselectivity.
Importantly,
the
reaction
pathway
was
regulated
by
simply
tuning
substituents,
achieving
substituent-directed
divergent
synthesis.
The
notable
features
of
this
transformation
include
readily
available
starting
materials,
green
conditions,
a
simple
workup
procedure,
high
bond-
ring-forming
efficiency,
diverse
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
Organic Letters,
Год журнала:
2020,
Номер
22(13), С. 5068 - 5073
Опубликована: Май 27, 2020
Reported
herein
is
an
unprecedented
multicomponent
one-pot
dearomative
multifunctionalization
of
commercially
available
azaarenes
through
in
situ
activation
strategy,
which
not
only
achieved
the
first
full
exploitation
reactive
sites
azaarenes,
but
also
accomplished
efficient
synthesis
bridged
hydrogenated
pyridines
and
(iso)quinolines
a
highly
regioselective
diastereoselective
manner.
In
addition,
we
could
successfully
realize
step-controlled
trifunctionalization
bifunctionalization
quinolines.
Chemical Science,
Год журнала:
2021,
Номер
12(46), С. 15389 - 15398
Опубликована: Янв. 1, 2021
A
novel
skeletal
remodeling
strategy
to
transform
chalcone-based
pyridinium
salts
into
structurally
intriguing
polycyclic
isoindolines
was
achieved
through
a
dearomative
ring-opening/ring-closing
sequence.
Chemical Communications,
Год журнала:
2020,
Номер
57(3), С. 359 - 362
Опубликована: Дек. 8, 2020
An
unexpected
construction
of
functionalized
π-extended
indolizine
polycycles
through
a
one-pot
two-step
process
comprising
the
base-promoted
dearomative
[3+2]
cycloaddition
and
DDQ-mediated
oxidative
decarbonylation
was
developed.
Chemical Science,
Год журнала:
2020,
Номер
12(2), С. 742 - 746
Опубликована: Ноя. 16, 2020
The
single
point
activation
of
pyridines,
using
an
electron-deficient
benzyl
group,
facilitates
the
ruthenium-catalysed
dearomative
functionalisation
a
range
electronically
diverse
pyridine
derivatives.
This
transformation
delivers
hydroxymethylated
piperidines
in
good
yields,
allowing
rapid
access
to
medicinally
relevant
small
heterocycles.
A
noteworthy
feature
this
work
is
that
paraformaldehyde
acts
as
both
hydride
donor
and
electrophile
reaction,
enabling
use
cheap
readily
available
feedstock
chemicals.
Removal
activating
group
can
be
achieved
readily,
furnishing
free
NH
compound
only
2
steps.
synthetic
utility
method
was
illustrated
with
synthesis
(±)-Paroxetine.
Chemical Communications,
Год журнала:
2023,
Номер
59(27), С. 4051 - 4054
Опубликована: Янв. 1, 2023
Dearomatization
reactions
provide
a
rapid
approach
to
construct
complicated
molecules
that
are
difficult
synthesize
by
traditional
methods
from
simple
aromatic
compounds.
Herein,
we
report
an
efficient
dearomative
[3+2]
cycloaddition
reaction
of
2-alkynyl
pyridines
with
diarylcyclopropenones,
leading
the
synthesis
densely
functionalized
indolizinones
in
moderate
good
yields
under
metal-free
conditions.
In
addition,
this
strategy
can
also
be
employed
cyclization
isoquinolines
access
variety
benzo-fused
indolizinones.
Density
functional
theory
(DFT)
calculations
revealed
appropriate
substituent
at
2-position
pyridine
is
crucial
dearomatization
process.
