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.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(5), С. 795 - 813
Опубликована: Фев. 23, 2024
ConspectusThe
selective
functionalization/transformation
of
ubiquitous
pyridine-fused
N-heteroarenes
is
a
practical
method
to
synthesize
structurally
novel
N-heterocycles,
which
important
for
the
development
medicines,
bioactive
agents,
agrochemicals,
materials,
ligands,
sensors,
pigments,
dyes,
etc.
However,
owing
thermodynamic
stability,
kinetic
inertness,
and
lone
electron
pair–induced
catalyst
deactivation
N-heteroarenes,
limited
strategies
(e.g.,
C–H
activation/functionalization,
electrophilic
substitution,
Minisci
reaction)
are
available
realize
synthetic
purpose
maintain
aromaticity
final
products.
Moreover,
relevant
transformations
have
limitations
such
as
needing
harsh
reaction
conditions,
requiring
preinstallation
specific
coupling
agents
containing
transformable
functionalities
or
directing
groups,
using
less
environmentally
benign
oxidants
and/or
acidic
activators,
poor
selectivity.
Herein,
considering
that
imines,
enamines,
radicals,
cyclic
amines
generated
during
reduction
precise
transformation
these
reductive
intermediates
offers
fundamental
basis
developing
tandem
reactions.
Our
group
revealed
slow
rate,
synergistic
catalysis,
controlled
electroreduction
effective
fulfilling
functionalization
N-heteroarenes.
Thus,
we
established
series
new
methods
provide
diverse
construction
modalities
functionalized
N-heterocycles.
The
striking
features
include
high
efficiency,
atom
economy,
use
readily
accessible
feedstocks
in
absence
flammable
pressurized
H2
gas,
alongside
promising
potential
obtained
N-heterocyclic
present
study
would
be
appealing
fields
organic
chemistry,
biomedical
functional
materials.
This
Account
describes
application
dearomatization
substrate-activating
reaction-initiating
modes
summarizes
via
alkylation,
arylation,
annulation
at
nitrogen,
α,
β,
other
remote
carbon
sites
achieved
over
past
8
years.
Details
regarding
reactions
their
plausible
mechanisms
perspectives
discussed.
We
hope
our
contributions
this
field
will
aid
further
tackle
intractable
challenges
area.
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
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(12), С. 8420 - 8434
Опубликована: Июнь 5, 2024
An
elegant
and
highly
concise
strategy
for
the
construction
of
coumarin-functionalized
pyrrolo[2,1-a]isoquinolines
from
available
propargylamines
isoquinolinium
N-ylides
has
been
disclosed.
In
this
reaction,
acted
as
a
C2
synthon
to
form
coumarin
ring
well
1,3-dipole
construct
pyrrole
in
single
pot.
This
cascade
process
involves
1,4-conjugate
addition/lactonization/1,3-dipolar
cycloaddition
four
chemical
bonds
(one
C–O
bond
three
C–C
bonds)
two
new
heterocyclic
skeletons.
Additionally,
most
these
compounds
showed
good
fluorescence
properties
exhibited
high
molar
extinction
coefficient
large
Stokes
shifts.
Chemical Communications,
Год журнала:
2022,
Номер
58(57), С. 7964 - 7967
Опубликована: Янв. 1, 2022
An
interrupted
dearomative
reduction
strategy
was
developed
to
transform
planar
chalcone-based
pyridinium
salts
into
structurally
intriguing
bridged
piperidines
in
a
completely
regio-
and
diastereoselective
manner.
This
reaction
proceeded
successfully
by
using
cheap
easily
accessible
NaBH4
as
the
reductant
under
mild
conditions
without
exclusion
of
oxygen
or
use
special
equipment.
Asian Journal of Organic Chemistry,
Год журнала:
2023,
Номер
12(12)
Опубликована: Окт. 9, 2023
Abstract
Metal
coordination
polymers
are
widely
applied
in
the
synthesis
of
heterocyclic
compounds
due
to
advantages
highly
dispersed
metal
active
sites,
low
cost
and
strong
designability.
Herein,
employing
9‐benzyl‐3,6‐di(
1H
‐pyrazol‐1‐yl)‐
9H
‐carbazole
(BPC)
as
a
ligand,
cadmium‐coordinated
polymer
compound
(Cd‐BPC)
was
facilely
prepared
by
solvothermal
method
characterized
energy
dispersive
spectrometer
(EDS),
flourier‐transform
infrared
spectroscopy
(FT‐IR),
scanning
electron
microscope
(SEM),
transmission
microscopy
(TEM)
X‐ray
photoelectron
spectrometry
(XPS).
Employing
Cd‐BPC
catalyst,
1,5‐benzodiazepine
derivatives
were
produced
with
relatively
high
yields
through
reaction
o
‐phenylenediamine
ketones,
alcohols.
Additionally,
could
be
reused
for
at
least
5
times
without
significant
decrease.
