ACS Catalysis,
Год журнала:
2024,
Номер
14(21), С. 16105 - 16114
Опубликована: Окт. 17, 2024
We
introduce
a
phosphine-catalyzed
cycloaddition
involving
unprecedented
long-range
intramolecular
proton
transfer,
facilitating
the
synthesis
of
nine-membered
heterocycles,
which
are
privileged
structures
in
natural
products,
as
well
potent
pharmacophores.
Experimental
and
computational
studies
revealed
that
enamide
tether
N-aromatic
zwitterion
directly
enables
regioselective
transfer
to
proceed
independently
outer-sphere
shuttling.
This
understanding
selective
has
led
improved
efficiency
regioselectivity
desired
1,9-proton
reaction
under
anhydrous
conditions,
thereby
advancing
development
higher-order
reactions.
Further
stereoselective
contraction
synthesized
cyclic
compounds
using
3-aza-Cope
rearrangement
demonstrates
synthetic
versatility
our
approach.
The
findings
this
study
not
only
advance
general
mechanism
but
also
broaden
its
practical
utility
various
chemical
fields.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(25)
Опубликована: Апрель 9, 2024
Abstract
A
formal
[4+2]
cycloaddition
reaction
of
ethynylethylene
carbonates
and
2‐aminophenols
has
been
developed
for
the
synthesis
3,4‐dihydro‐2
H
‐benzo[
b
][1,4]oxazines
bearing
quaternary
carbon
atoms.
The
features
mild
conditions,
good
functional
group
compatibility
yields.
Furthermore,
when
using
chiral
PyBox
ligand,
this
strategy
could
also
achieve
asymmetric
][1,4]oxazines.
Application
studies
indicated
that
hydroxymethyl
final
products
was
an
excellent
can
be
further
modified
easily.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(15), С. 10551 - 10556
Опубликована: Июль 17, 2024
Palladium-catalyzed
dipolar
cycloaddition
reactions
represent
an
efficient
strategy
for
the
construction
of
cyclic
compounds,
with
development
novel
precursors
being
a
key
focus.
In
this
study,
new
type
precursor
was
synthesized
through
assembly
vinylethylene
carbonate
unit
and
tetrahydronaphthalene
skeleton.
This
can
undergo
[3
+
2],
[5
4],
2]
reactions,
leading
to
tetrahydronaphthalene-fused
oxazolidin-2-ones,
1,5-oxazonines,
tetrahydrooxepines.
general,
all
these
exhibited
good
reaction
efficiency
functional
group
tolerance.
ACS Catalysis,
Год журнала:
2024,
Номер
14(21), С. 16105 - 16114
Опубликована: Окт. 17, 2024
We
introduce
a
phosphine-catalyzed
cycloaddition
involving
unprecedented
long-range
intramolecular
proton
transfer,
facilitating
the
synthesis
of
nine-membered
heterocycles,
which
are
privileged
structures
in
natural
products,
as
well
potent
pharmacophores.
Experimental
and
computational
studies
revealed
that
enamide
tether
N-aromatic
zwitterion
directly
enables
regioselective
transfer
to
proceed
independently
outer-sphere
shuttling.
This
understanding
selective
has
led
improved
efficiency
regioselectivity
desired
1,9-proton
reaction
under
anhydrous
conditions,
thereby
advancing
development
higher-order
reactions.
Further
stereoselective
contraction
synthesized
cyclic
compounds
using
3-aza-Cope
rearrangement
demonstrates
synthetic
versatility
our
approach.
The
findings
this
study
not
only
advance
general
mechanism
but
also
broaden
its
practical
utility
various
chemical
fields.
