Angewandte Chemie,
Год журнала:
2022,
Номер
134(27)
Опубликована: Май 13, 2022
Abstract
Herein
we
disclose
a
mild
protocol
for
the
reductive
functionalisation
of
quinolinium
and
isoquinolinium
salts.
The
reaction
proceeds
under
transition‐metal‐free
conditions
as
well
rhodium
catalysis
with
very
low
catalyst
loadings
(0.01
mol
%)
uses
inexpensive
formic
acid
terminal
reductant.
A
wide
range
electrophiles,
including
enones,
imides,
unsaturated
esters
sulfones,
β‐nitro
styrenes
aldehydes
are
intercepted
by
in
situ
formed
enamine
species
forming
large
variety
substituted
tetrahydro(iso)quinolines.
Electrophiles
incorporated
at
C‐3
C‐4
position
quinolines
isoquinolines
respectively,
providing
access
to
substitution
patterns
which
not
favoured
electrophilic
or
nucleophilic
aromatic
substitution.
Finally,
this
reactivity
was
exploited
facilitate
three
types
annulation
reactions,
giving
rise
complex
polycyclic
products
formal
[3+3]
[4+2]
cycloaddition.
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.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(27)
Опубликована: Май 13, 2022
Herein
we
disclose
a
mild
protocol
for
the
reductive
functionalisation
of
quinolinium
and
isoquinolinium
salts.
The
reaction
proceeds
under
transition-metal-free
conditions
as
well
rhodium
catalysis
with
very
low
catalyst
loadings
(0.01
mol
%)
uses
inexpensive
formic
acid
terminal
reductant.
A
wide
range
electrophiles,
including
enones,
imides,
unsaturated
esters
sulfones,
β-nitro
styrenes
aldehydes
are
intercepted
by
in
situ
formed
enamine
species
forming
large
variety
substituted
tetrahydro(iso)quinolines.
Electrophiles
incorporated
at
C-3
C-4
position
quinolines
isoquinolines
respectively,
providing
access
to
substitution
patterns
which
not
favoured
electrophilic
or
nucleophilic
aromatic
substitution.
Finally,
this
reactivity
was
exploited
facilitate
three
types
annulation
reactions,
giving
rise
complex
polycyclic
products
formal
[3+3]
[4+2]
cycloaddition.
Organic Letters,
Год журнала:
2023,
Номер
25(4), С. 614 - 618
Опубликована: Янв. 23, 2023
A
simple
method
for
the
C-4
alkylation
of
isoquinolines
is
described
using
benzoic
acid
as
a
nucleophilic
reagent
and
vinyl
ketones
an
electrophile.
The
reaction
shows
tolerance
substitution
at
C-3,
C-5-C-8
positions
well
allowing
some
variation
ketone
electrophiles.
products
contain
carbonyl
that
can
act
synthetic
handle
further
manipulations
giving
esters,
amines,
or
alkyl
products.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(49)
Опубликована: Окт. 20, 2023
Nitrogen
heterocycles
play
a
vital
role
in
pharmaceuticals
and
natural
products,
with
the
six-membered
aromatic
aliphatic
architectures
being
commonly
used.
While
synthetic
methods
for
N-heterocycles
are
well-established,
synthesis
of
their
functionalized
analogues,
particularly
piperidine
derivatives,
poses
significant
challenge.
In
that
regard,
we
propose
stepwise
dearomative
functionalization
reaction
construction
highly
decorated
derivatives
diverse
functional
handles.
We
also
discuss
challenges
related
to
site-selectivity,
regio-
diastereoselectivity,
provide
insights
into
mechanism
through
mechanistic
studies
density
theory
computations.
Synthesis,
Год журнала:
2024,
Номер
56(16), С. 2483 - 2498
Опубликована: Янв. 30, 2024
Abstract
The
Brook
rearrangement
is
a
valuable
synthetic
tool
that
facilitates
the
controlled
construction
of
complex
molecules.
Conventionally,
it
generates
carbanion
intermediates
utilized
in
subsequent
functionalization
reactions.
In
this
review,
we
will
explore
recent
advancements
extend
beyond
traditional
Specifically,
highlight
its
involvement
unusual
bond
cleavage,
annulation
reactions,
and
dearomatization
efforts.
novelty
underscored
by
showcasing
most
applications.
1
Introduction
2
Novel
Synthetic
Pathways
Involving
Rearrangement
2.1
C–C
C–X
Bond
Formation
2.2
Cleavage
2.3
Stereodefined
Substituted
Silyl
Enol
Allenol
Ethers
2.4
Annulation
Reactions
2.5
Dearomatization
3
Applications
4
Conclusion
Chemical Communications,
Год журнала:
2023,
Номер
59(46), С. 7088 - 7091
Опубликована: Янв. 1, 2023
The
difficulty
in
isolating
cyclic
enamines
emanating
from
their
intrinsic
instability
has
impeded
exploration
cycloaddition
reactions.
Here,
we
achieved
a
metal-free
domino
reaction
providing
quinoline
and
isoquinoline-derived
amidines
by
the
of
azides
with
situ
generated
via
dearomatization.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
29(5)
Опубликована: Ноя. 3, 2022
Organic
ultralong
room-temperature
phosphorescence
(RTP)
materials
have
attracted
great
attention
for
their
wide
applications
in
optoelectronic
devices
and
bioimaging.
However,
the
development
of
these
remains
a
challenging
task,
partially
due
to
lack
rational
molecular
design
strategies
unclear
luminescence
mechanisms.
Herein,
we
present
method
facile
access
structurally
diverse
substituted
1-aminoisoquinoline
derivatives
through
copper-catalyzed
one-pot
three-component
coupling
reaction
that
provides
promising
approach
rapidly
assemble
library
1-aminoisoquinolines
exploring
regularity
host-guest
doped
system.
A
series
RTP
with
wide-ranging
lifetimes
from
4.4
299.3
ms
were
constructed
by
doping
various
isoquinolines
into
benzophenone
(BP).
Furthermore,
4
r/BP
nanoparticles
could
be
used
in-vivo
imaging
signal-to-noise
ratio
value
as
high
32,
revealing
potential
isoquinoline
framework
construction
high-performance
materials.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(8), С. 1820 - 1826
Опубликована: Фев. 7, 2024
Abstract
Rh(I)‐catalyzed
C8‐selective
C−H
alkenylation
and
arylation
of
1,2,3,4‐tetrahydroquinolines
with
alkenyl
aryl
carboxylic
acids
under
microwave
assistance
have
been
realized.
Using
[Rh(CO)
2
(acac)]
as
the
catalyst
Piv
O
acid
activator,
undergo
decarbonylative
a
wide
range
acids,
affording
C8‐alkenylated
or
arylated
1,2,3,4‐tetrahydroquinolines.
This
method
enables
synthesis
that
would
otherwise
be
difficult
to
access
by
means
conventional
protocols.
Moreover,
this
catalytic
system
also
works
well
in
acids.
The
activity
strongly
depends
on
choice
N
‐directing
group,
readily
installable
removable
‐(2‐pyrimidyl)
group
being
optimal.
pathway
is
elucidated
mechanistic
experiments.
