Regio‐ and Diastereoselective Synthesis of Polysubstituted Piperidines Enabled by Boronyl Radical‐Catalyzed (4+2) Cycloaddition
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(38)
Published: June 26, 2024
Piperidines
are
widely
present
in
small
molecule
drugs
and
natural
products.
Despite
many
methods
have
been
developed
for
their
synthesis,
new
approaches
to
polysubstituted
piperidines
highly
desirable.
This
work
presents
a
radical
(4+2)
cycloaddition
reaction
synthesis
of
featuring
dense
substituents
at
3,4,5-positions
that
not
readily
accessible
by
known
methods.
Using
commercially
available
diboron(4)
compounds
4-phenylpyridine
as
the
catalyst
precursors,
boronyl
radical-catalyzed
between
3-aroyl
azetidines
various
alkenes,
including
previously
unreactive
1,2-di-,
tri-,
tetrasubstituted
has
delivered
generally
high
yield
diastereoselectivity.
The
also
features
modularity,
atom
economy,
broad
substrate
scope,
metal-free
conditions,
simple
catalysts
operation.
utilization
products
demonstrated
selective
transformations.
A
plausible
mechanism,
with
ring-opening
azetidine
rate-limiting
step,
proposed
based
on
experimental
computational
results.
Language: Английский
Broad-Scope (3 + 2) Cycloaddition of Cyclopropanes and Alkynes Enabled by Boronyl Radical Catalysis
Jingru Wen,
No information about this author
Zhengwei Ding,
No information about this author
Pengfei Li
No information about this author
et al.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(33), P. 7021 - 7025
Published: Aug. 14, 2024
Cyclopentene
skeletons
are
ubiquitous
in
natural
products
and
small
molecule
drugs.
The
(3
+
2)
cycloaddition
of
cyclopropanes
alkynes
represents
an
efficient
atom-economic
strategy
for
synthesizing
these
structures.
However,
the
types
substituents
on
cyclopropane
alkyne
used
previous
works
show
evident
limitations,
restricting
application
this
type
reaction
to
some
extent.
Herein,
we
report
a
broad-scope
catalyzed
by
boronyl
radicals.
In
method,
various
substrates,
such
as
mono-,
di-,
tri-,
tetrasubstituted
cyclopropanes,
well
mono-
disubstituted
alkynes,
were
compatible
with
up
98%
isolated
yield.
Language: Английский
Recent Advancements in Metal‐Free Catalysis for Cyclopropane Ring Cleavage
ChemistrySelect,
Journal Year:
2025,
Volume and Issue:
10(9)
Published: March 1, 2025
Abstract
Over
the
last
decade,
there
have
been
notable
advances
in
field
of
ring
opening
reaction
numerous
cyclopropane
derivatives
under
metal‐free
conditions
including
donor–acceptor
cyclopropanes,
acceptor‐activated
alkylidenecyclopropanes,
cyclopropyl
alcohols,
and
vinylidenecyclopropanes.
This
review
article
aims
to
offer
a
comprehensive
overview
on
cleavage
reactions
cyclopropanes
using
Bronsted
Lewis
acids,
organic
inorganic
bases,
TCT‐DMF,
ionic
liquids
etc.
Photoinduced
catalyst‐free
are
also
accentuated
this
review.
Language: Английский
Regio‐ and Diastereoselective Synthesis of Polysubstituted Piperidines Enabled by Boronyl Radical‐Catalyzed (4+2) Cycloaddition
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(38)
Published: June 26, 2024
Abstract
Piperidines
are
widely
present
in
small
molecule
drugs
and
natural
products.
Despite
many
methods
have
been
developed
for
their
synthesis,
new
approaches
to
polysubstituted
piperidines
highly
desirable.
This
work
presents
a
radical
(4+2)
cycloaddition
reaction
synthesis
of
featuring
dense
substituents
at
3,4,5‐positions
that
not
readily
accessible
by
known
methods.
Using
commercially
available
diboron(4)
compounds
4‐phenylpyridine
as
the
catalyst
precursors,
boronyl
radical‐catalyzed
between
3‐aroyl
azetidines
various
alkenes,
including
previously
unreactive
1,2‐di‐,
tri‐,
tetrasubstituted
has
delivered
generally
high
yield
diastereoselectivity.
The
also
features
modularity,
atom
economy,
broad
substrate
scope,
metal‐free
conditions,
simple
catalysts
operation.
utilization
products
demonstrated
selective
transformations.
A
plausible
mechanism,
with
ring‐opening
azetidine
rate‐limiting
step,
proposed
based
on
experimental
computational
results.
Language: Английский
A Radical Hydrohaloalkylation of the Ligand Sphere of a Chiral Dehydroalanine Ni(II) Complex: An Asymmetric Route to Halogenated α-Amino Acid Derivatives
Nadezhda V. Stoletova,
No information about this author
Alexander F. Smol’yakov,
No information about this author
Andrey A. Tyutyunov
No information about this author
et al.
Tetrahedron Chem,
Journal Year:
2024,
Volume and Issue:
unknown, P. 100118 - 100118
Published: Dec. 1, 2024
Language: Английский