Angewandte Chemie,
Год журнала:
2023,
Номер
135(49)
Опубликована: Окт. 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.
Molecules,
Год журнала:
2023,
Номер
28(17), С. 6186 - 6186
Опубликована: Авг. 22, 2023
1,2-
and
1,4-dihydropyridines
N-substituted
2-pyridones
are
very
important
structural
motifs
due
to
their
synthetic
versatility
vast
presence
in
a
variety
of
alkaloids
bioactive
molecules.
In
this
article,
we
gather
summarize
the
catalytic
stereoselective
synthesis
partially
hydrogenated
pyridines
pyridones
via
dearomative
reactions
pyridine
derivatives
up
mid-2023.
The
material
is
fundamentally
organized
according
type
reactivity
(electrophilic/nucleophilic)
nucleus.
further
sub-divided
taking
into
account
nucleophilic
species
when
dealing
with
electrophilic
considering
manifold
behaving
as
nucleophiles
at
nitrogen
site.
latter
more
recent
approach
allows
for
an
unconventional
entry
chiral
2-
4-pyridones
non-racemic
form.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(35), С. 24708 - 24715
Опубликована: Авг. 20, 2024
We
describe
a
Rh(I)
catalyzed
asymmetric
ring
opening
of
racemic
vinyl
cyclopropanes
using
aryl
boronic
acids
as
C-nucleophiles.
When
ferrocene-based
chiral
bisphosphines
are
used
ligands,
the
products
obtained
with
regioselectivities
typically
99:1
r.r.
and
ee's
generally
between
88
96%.
A
wide
range
can
be
used,
converted
into
variety
targets.
Preliminary
mechanistic
studies
indicate
that
Zn(OTf)2
plays
significant
role
in
reaction
by
promoting
rhodium-ligand
complex
formation
accelerating
reaction.
expect
this
method
these
insights
to
useful
development
new
methods.
In
this
study,
we
describe
a
generally
straightforward
methodology
for
the
catalytic
synthesis
of
chiral
aminopiperidine
from
pyridine
and
azoles.
The
key
step
was
palladium-catalyzed
regioselective
N–H
insertion
into
double
bond
1,2-dihydropyridine.
This
hydroamination
exhibits
wide
substrate
scope
functional
group
compatibility.
Mechanistic
study
revealed
that
C═C
followed
cis
addition.
utility
protocol
demonstrated
by
diverse
functionalization
enamine
bond.
Herein,
an
approach
to
a
wide
range
of
chiral
3-substituted
δ-lactams
from
reductive
coupling
Csp2-hybridized
organohalides
and
3-chloro-δ-lactams
was
described,
the
products
are
versatile
precursors
for
accessing
enantioenriched
piperidines.
The
utility
reaction
highlighted
by
economic
synthesis
Preclamol
Niraparib.
Notably,
modified
Bilm
ligands
were
found
be
key
factor
reactivity
enantioselectivity.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(36)
Опубликована: Июль 18, 2023
Unprotected
cis-2,3-diarylpiperidines
are
synthesized
through
an
unprecedented
palladium-catalyzed
cross-coupling
reaction
between
aryl
halides
and
elusive
endocyclic
1-azaallyl
anions.
These
intermediates
generated
in
situ
by
the
deprotonation
of
2-aryl-1-piperideines,
precursors
that
readily
prepared
two
operations
from
simple
piperidines.
An
asymmetric
version
this
with
(2R,
3R)-iPr-BI-DIME
as
ligand
provides
products
moderate
to
good
yields
enantioselectivities.
This
study
significantly
expands
synthetic
utility
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.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(48)
Опубликована: Окт. 11, 2023
A
copper-catalyzed
dearomative
alkynylation
of
pyridines
is
reported
with
excellent
regio-
and
enantioselectivities.
The
synthetically
valuable
enantioenriched
2-alkynyl-1,2-dihydropyridine
products
afforded
are
generated
from
the
readily
available
feedstock,
pyridine,
commercially
terminal
alkynes.
three-component
reaction
between
a
alkyne,
methyl
chloroformate
employs
copper
chloride
StackPhos,
chiral
biaryl
P,N-
ligand,
as
catalytic
system.
Under
mild
conditions,
desired
1,2-addition
delivered
in
up
to
99
%
yield
regioselectivity
ratios
25
:
1
enantioselectivities
values
ee.
Activated
non-activated
alkynes
containing
wide
range
functional
groups
well
tolerated.
Even
acetylene
gas
mono-alkynylated
high
Application
methodology
an
efficient
enantioselective
synthesis
piperidine
indolizidine,
coniceine,
reported.
Organic Letters,
Год журнала:
2023,
Номер
25(50), С. 8987 - 8991
Опубликована: Дек. 7, 2023
We
report
a
rhodium-catalyzed
asymmetric
addition
of
aryl
and
alkenyl
boronic
acids
to
quinoxalinium
salts
that
generates
dihydroquinoxalines
with
high
enantioselectivity.
Functionalization
the
reaction
products,
dihydroquinoxaline,
allows
preparation
tetrahydroquinoxalines
various
substitution
patterns.
Organic Letters,
Год журнала:
2023,
Номер
25(51), С. 9087 - 9091
Опубликована: Дек. 19, 2023
The
stereoselective
preparation
of
functionalized
[1,2,4]triazolo[4,3-a]pyridines
from
N-tosylhydrazones
and
pyridines
was
developed
through
the
dearomatization
pyridines.
current
transformation
features
good
step-
atom-economy,
high
diastereoselectivity,
efficient
formation
four
new
carbon-heteroatom
bonds
in
corresponding
product
tetrahydro
