Molecules,
Год журнала:
2022,
Номер
27(23), С. 8517 - 8517
Опубликована: Дек. 3, 2022
Axially
chiral
heterobiaryl
frameworks
are
privileged
structures
in
many
natural
products,
pharmaceutically
active
molecules,
and
ligands.
Therefore,
a
variety
of
approaches
for
constructing
these
skeletons
have
been
developed.
Among
them,
de
novo
synthesis,
due
to
its
highly
convergent
superior
atom
economy,
serves
as
promising
strategy
access
challenging
scaffolds
including
C-N,
C-C,
N-N
axes.
So
far,
several
elegant
reviews
on
the
synthesis
axially
disclosed,
however,
atroposelective
construction
subunits
by
was
rarely
covered.
Herein,
we
summarized
recent
advances
catalytic
asymmetric
scaffold
via
synthetic
strategies.
The
related
mechanism,
scope,
applications
were
also
included.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(15)
Опубликована: Фев. 7, 2023
This
study
establishes
the
first
organocatalytic
enantioselective
synthesis
of
axially
chiral
N,N'-bisindoles
via
phosphoric
acid-catalyzed
formal
(3+2)
cycloadditions
indole-based
enaminones
as
novel
platform
molecules
with
2,3-diketoesters,
where
de
novo
indole-ring
formation
is
involved.
Using
this
new
strategy,
various
were
synthesized
in
good
yields
and
excellent
enantioselectivities
(up
to
87
%
yield
96
ee).
More
importantly,
class
exhibited
some
degree
cytotoxicity
toward
cancer
cells
was
derived
into
phosphine
ligands
high
catalytic
activity.
provides
a
strategy
for
using
asymmetric
organocatalysis
realize
applications
such
scaffolds
medicinal
chemistry
catalysis.
Precision Chemistry,
Год журнала:
2024,
Номер
2(5), С. 208 - 220
Опубликована: Апрель 23, 2024
The
catalytic
asymmetric
diastereodivergent
synthesis
of
axially
chiral
2-alkenylindoles
was
established
via
phosphoric
acid-catalyzed
addition
reactions
C3-unsubstituted
with
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(8)
Опубликована: Дек. 29, 2023
Abstract
In
the
chemistry
community,
catalytic
asymmetric
synthesis
of
furan‐based
compounds
bearing
both
axial
and
central
chirality
has
proven
to
be
a
significant
but
challenging
issue
owing
importance
difficulty
in
constructing
such
frameworks.
this
work,
we
have
realized
first
five‐five‐membered
via
organocatalytic
(2+4)
annulation
achiral
furan‐indoles
with
2,3‐indolyldimethanols
uncommon
regioselectivity.
By
strategy,
furan‐indole
were
synthesized
high
yields
excellent
regio‐,
diastereo‐,
enantioselectivities.
Moreover,
theoretical
calculations
conducted
provide
an
in‐depth
understanding
reaction
pathway,
activation
mode,
origin
selectivity.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(27)
Опубликована: Март 6, 2023
Atropisomeric
heterobiaryls
play
a
vital
role
in
natural
products,
chiral
ligands,
organocatalysts,
and
other
research
fields,
which
have
aroused
great
interest
from
chemists
recent
years.
Until
now,
growing
number
of
optically
active
based
on
indole,
quinoline,
isoquinoline,
pyridine,
pyrrole,
azole,
benzofuran
skeletons
been
successfully
synthesized
through
metal
or
organic
catalytic
cross-coupling,
functionalization
prochiral
racemic
heterobiaryls,
ring
formation.
Among
different
strategies
for
the
atroposelective
synthesis
strategy
formation
has
become
tool
toward
this
goal.
In
review,
we
summarize
enantioselective
axially
approaches,
such
as
cycloaddition,
cyclization,
chirality
conversion.
Meanwhile,
reaction
mechanism
corresponding
applications
are
also
discussed.
European Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 2, 2025
Abstract
This
review
collects
the
recent
developments
in
synthesis
of
chiral
heterocycles
through
enantioselective
silver‐catalyzed
transformations
published
since
2018.
It
demonstrates
power
silver
catalysts
as
special
mild
Lewis
acids
to
provide
an
impressive
diversity
reaction
pathways,
such
1,3‐dipolar
cycloadditions,
various
types
cyclizations,
along
with
a
wide
variety
more
complex
domino/tandem
reactions,
allowing
many
novel
heterocyclic
products
be
achieved
high
enantioselectivities.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(42)
Опубликована: Авг. 30, 2022
Atroposelective
electrophilic
sulfenylation
of
N-aryl
aminoquinone
derivatives
has
been
achieved
for
the
first
time.
This
transformation
is
enabled
by
a
new
chiral
6,6'-disubstituted
SPINOL-derived
sulfide
catalyst,
which
was
synthesized
and
then
successfully
explored
catalyzing
enantioselective
reactions.
Various
axially
sulfur-containing
diarylamine
were
readily
obtained
in
moderate
to
excellent
yields
with
enantioselectivities.
A
class
relatively
flexible
stereogenic
C-N
axes
easily
constructed.
The
experimental
results
computational
study
suggested
that
an
intramolecular
N-H⋅⋅⋅S
hydrogen
bond
important
stability
axis,
consistent
our
hypothesis.
Density
functional
theory
calculations
revealed
origin
atroposelectivity
underscored
importance
catalyst
rigidity
this
reaction.
ACS Catalysis,
Год журнала:
2022,
Номер
13(1), С. 659 - 664
Опубликована: Дек. 22, 2022
A
highly
enantioselective
biocatalytic
dynamic
kinetic
resolution
(DKR)
of
configurationally
labile
N-arylindole
aldehydes
is
described.
The
DKR
proceeds
by
atroposelective
bioreduction
the
carbonyl
group
catalyzed
commercial
ketoreductases
(KREDs),
thus
affording
corresponding
axially
chiral
aminoalcohols,
with
excellent
conversions
and
optical
purities.
strategy
relies
on
racemization
stereogenic
axis
that
takes
place
thanks
to
a
transient
Lewis
pair
interaction
between
NMe2
aldehyde
groups.
This
protocol
features
broad
substrate
scope
under
very
mild
conditions.
Organic Letters,
Год журнала:
2023,
Номер
25(3), С. 522 - 527
Опубликована: Янв. 18, 2023
Atropisomeric
indoles
widely
exist
in
natural
products,
pharmaceuticals,
functional
materials,
and
catalysts
for
their
featured
biological
activities,
photoelectric
properties,
catalytic
while
facile
de
novo
construction
of
this
motif
remains
underexplored.
Herein,
we
report
a
chiral
silver
phosphate-catalyzed
direct
5-endo-dig
nucleophilic
cyclization
2-alkynylanilins
under
mild
conditions,
affording
various
C-C
axially
2-arylindoles
high
to
excellent
yields
enantioselectivities.
Control
experiments
implied
the
cooperative
catalysis
AgOAc
phosphoric
acid,
wherein
former
accelerated
desired
transformation
latter
improved
enantioselectivity.
In
addition,
as
first
example
silver-catalyzed
enantioselective
synthesis
indole
skeletons,
synthetic
applications
products'
thermal
stability
have
been
investigated.
Chemical Science,
Год журнала:
2023,
Номер
14(19), С. 5182 - 5187
Опубликована: Янв. 1, 2023
The
copper-catalyzed
azide-alkyne
cycloaddition
(CuAAC)
reaction
is
regarded
as
a
prime
example
of
"click
chemistry",
but
the
asymmetric
click
internal
alkynes
still
remains
challenging.
A
new
Rh-catalyzed
N-alkynylindoles
with
azides
was
developed,
providing
atroposelective
access
to
C-N
axially
chiral
triazolyl
indoles,
type
heterobiaryl,
excellent
yields
and
enantioselectivity.
This
approach
efficient,
mild,
robust
atom-economic,
features
very
broad
substrate
scope
easily
available
Tol-BINAP
ligands.
