Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
134(27)
Published: May 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.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
unknown
Published: Sept. 13, 2023
Abstract
Quinobenzazepines
are
useful
in
medicinal
chemistry,
but
their
synthesis
is
very
challenging.
Herein,
we
designed
and
synthesized
a
range
of
multi‐functional
chalcone‐based
quinolinium
salts;
synthetic
application
the
rapid
straightforward
construction
quinobenzazepines
was
successfully
explored.
A
wide
oxa‐bridged
quinobenzazepine
polycycles
were
afforded
serendipitously
through
dearomative
cascade
reaction
our
newly
developed
salts
acetylacetone.
This
strategy
features
high
bond‐
ring‐forming
efficiency
complete
regio‐
diastereoselective
control.
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(49)
Published: Oct. 20, 2023
Abstract
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.
Asian Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
13(1)
Published: Dec. 11, 2023
Abstract
This
study
reports
the
first
synthesis
of
tetrahydroquinaldic
and
tetrahydropicolinic
amides
using
readily
available
quinolines
pyridines
through
dearomative
difunctionalization
hydrolysis
under
transition‐metal‐
reductant‐free
conditions.
The
prepared
amide
products
could
be
easily
oxidized
to
corresponding
quinaldic
picolinic
amides.
Furthermore,
chemical
reactivity
group
has
been
explored
develop
convenient
methods
for
their
conversion
other
common
organic
functional
groups.
Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
134(27)
Published: May 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.
