The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
88(12), С. 7684 - 7702
Опубликована: Ноя. 23, 2022
An
axially
chiral
indolyl-pyrroloindole
scaffold,
a
new
member
of
indole-based
scaffolds,
has
been
designed,
and
the
catalytic
asymmetric
construction
this
scaffold
established
by
strategy
organocatalytic
(2
+
3)
cycloaddition
3,3'-bisindoles
with
isoindolinone-based
propargylic
alcohols.
By
approach,
series
derivatives
bearing
both
axial
chirality
central
were
synthesized
in
high
yields
excellent
diastereo-
enantioselectivities
(up
to
95%
yield,
91:9
dr,
99%
ee).
This
reaction
not
only
realizes
first
n)
as
1,2-dinucleophiles
but
also
provides
for
atroposelective
scaffolds
five-five-membered
rings,
thus
solving
challenges
constructing
class
scaffolds.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 23, 2024
Abstract
Catalytic
enantioselective
preparation
of
alkene
atropisomers
with
multiple
stereogenic
elements
and
discovery
their
applications
have
become
significant
but
challenging
issues
in
the
scientific
community
due
to
unique
structures
this
class
atropisomers.
We
herein
report
first
catalytic
atroposelective
cyclopentenyl[
b
]indoles,
a
new
kind
atropisomers,
point
axial
chirality
via
an
unusual
rearrangement
reaction
3‐indolylmethanols
under
asymmetric
organocatalysis.
Notably,
novel
type
promising
developing
chiral
ligands
or
organocatalysts,
discovering
antitumor
drug
candidates
fluorescence
imaging
materials.
Moreover,
theoretical
calculations
elucidated
possible
mechanism
non‐covalent
interactions
control
enantioselectivity.
This
approach
offers
synthetic
strategy
for
elements,
represents
3‐indolylmethanols,
which
will
advance
chemistry
indole
chemistry.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Фев. 15, 2025
Methods
for
catalytically
constructing
of
N–N
axially
chiral
scaffolds
have
garnered
significant
attention
since
such
compounds
are
widely
present
in
natural
products,
bioactive
molecules,
and
organic
materials.
Herein,
we
report
a
highly
diastereoselective
enantioselective
organocatalyzed
[4
+
1]
annulation
method
synthesizing
diverse
valuable
isoindolinones
that
possessing
axial
central
chiralities.
This
methodology
uses
phosphoric
acid
as
bifunctional
catalyst
to
promote
cascade
sequence
involving
two
nucleophilic
additions,
dehydration,
dearomatization
processes.
Control
experiments
DFT
calculations
revealed
possible
mechanism
which
the
stereoselectivity-determining
step
is
likely
involve
irreversible
formation
hydroxy
biaryl
intermediate.
Additionally,
preliminary
biological
activity
studies
showed
some
these
potential
suppressing
tumor-cell
proliferation.
attention.
Here,
authors
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
88(12), С. 7684 - 7702
Опубликована: Ноя. 23, 2022
An
axially
chiral
indolyl-pyrroloindole
scaffold,
a
new
member
of
indole-based
scaffolds,
has
been
designed,
and
the
catalytic
asymmetric
construction
this
scaffold
established
by
strategy
organocatalytic
(2
+
3)
cycloaddition
3,3'-bisindoles
with
isoindolinone-based
propargylic
alcohols.
By
approach,
series
derivatives
bearing
both
axial
chirality
central
were
synthesized
in
high
yields
excellent
diastereo-
enantioselectivities
(up
to
95%
yield,
91:9
dr,
99%
ee).
This
reaction
not
only
realizes
first
n)
as
1,2-dinucleophiles
but
also
provides
for
atroposelective
scaffolds
five-five-membered
rings,
thus
solving
challenges
constructing
class
scaffolds.
