ACS Catalysis,
Год журнала:
2024,
Номер
15(1), С. 255 - 264
Опубликована: Дек. 16, 2024
The
catalytic
asymmetric
synthesis
of
functionalized
C2-quaternary
indoline
scaffolds
has
garnered
significant
attention
in
organic
and
drug
discovery
due
to
the
inherent
challenges
potential
applications.
Herein,
we
present
a
facile
approach
utilizing
Pd-catalyzed
intramolecular
decarboxylative
amination
vinyl
benzoxazepinones,
leading
efficient
construction
challenging
chiral
2-vinyl-2-aryl/alkyl
frameworks
good
yields
with
high
enantioselectivities
(>50
examples,
up
83%
yield
97%
ee).
Furthermore,
these
indolines
can
be
readily
scaled
further
modified
access
complex
polycyclic
structures.
We
also
synthesized
several
indoline-based
ligands
that
exhibit
promising
efficiency
as
catalysts
reactions.
Computational
studies
provided
insight
into
inner-sphere
mechanism.
Alkyne-functionalized
oxetanes
are
presented
as
versatile
substrates
that
in
combination
with
amine
reagents
can
be
transformed
into
structurally
diverse,
chiral
γ-amino
alcohols
featuring
a
tetrasubstituted
tertiary
stereocenter
under
Cu
catalysis.
Control
experiments
demonstrate
the
privileged
nature
of
these
oxetane
precursors
terms
yield
and
asymmetric
induction
levels
developed
protocol,
postsynthetic
modifications
offer
an
easy
way
to
access
more
advanced
synthons.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(39)
Опубликована: Май 13, 2024
(Z)-alkenes
are
useful
synthons
but
thermodynamically
less
stable
than
their
(E)-isomers
and
typically
more
difficult
to
prepare.
The
synthesis
of
1,4-hetero-bifunctionalized
is
particularly
challenging
due
the
inherent
regio-
stereoselectivity
issues.
Herein
we
demonstrate
a
general,
chemoselective
direct
(Z)-2-butene-1,4-diol
monoesters.
protocol
operates
within
Pd-catalyzed
decarboxylative
acyloxylation
regime
involving
vinyl
ethylene
carbonates
(VECs)
various
carboxylic
acids
as
reaction
partners
under
mild
operationally
attractive
conditions.
newly
developed
process
allows
access
structurally
diverse
pool
monoesters
in
good
yields
with
excellent
stereoselectivity.
Various
synthetic
transformations
obtained
how
these
great
use
rapidly
diversify
portfolio
formal
desymmetrized
(Z)-alkenes.
ACS Catalysis,
Год журнала:
2024,
Номер
15(1), С. 255 - 264
Опубликована: Дек. 16, 2024
The
catalytic
asymmetric
synthesis
of
functionalized
C2-quaternary
indoline
scaffolds
has
garnered
significant
attention
in
organic
and
drug
discovery
due
to
the
inherent
challenges
potential
applications.
Herein,
we
present
a
facile
approach
utilizing
Pd-catalyzed
intramolecular
decarboxylative
amination
vinyl
benzoxazepinones,
leading
efficient
construction
challenging
chiral
2-vinyl-2-aryl/alkyl
frameworks
good
yields
with
high
enantioselectivities
(>50
examples,
up
83%
yield
97%
ee).
Furthermore,
these
indolines
can
be
readily
scaled
further
modified
access
complex
polycyclic
structures.
We
also
synthesized
several
indoline-based
ligands
that
exhibit
promising
efficiency
as
catalysts
reactions.
Computational
studies
provided
insight
into
inner-sphere
mechanism.
