Chemical Synthesis,
Год журнала:
2023,
Номер
3(1), С. 6 - 6
Опубликована: Янв. 1, 2023
In
recent
years,
it
has
become
an
urgent
task
to
design
new
types
of
indole-based
platform
molecules
for
Nazarov-type
cyclizations
and
develop
organocatalytic
synthesizing
indole
derivatives.
To
fulfill
this
task,
in
work,
by
changing
the
alkynyl
terminal
substituent
from
t-Bu
aryl
group,
reactivity
3-alkynyl-2-indolylmethanols
is
modulated
serve
as
competent
substrates
Brønsted
acid-catalyzed
cyclization.
Based
on
reactivity,
first
cyclization
aryl-substituted
with
2-naphthols
accomplished,
leading
efficient
construction
a
class
axially
chiral
3,
4-dihydrocyclopenta[b]indole
scaffolds.
This
preliminary
investigation
asymmetric
provides
optional
strategy
atroposelective
cyclopenta[b]indole
addition,
preparation
optical
purity
established
through
resolution,
which
could
complementary
method
catalytic
approaches.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(47)
Опубликована: Сен. 15, 2022
Enantioselective
C-H
activation
has
surfaced
as
a
transformative
toolbox
for
the
efficient
assembly
of
chiral
molecules.
However,
despite
major
advances
in
rhodium
and
palladium
catalysis,
ruthenium(II)-catalyzed
enantioselective
thus
far
largely
proven
elusive.
In
contrast,
we
herein
report
on
highly
regio-,
diastereo-
alkylation.
The
key
to
success
was
represented
by
identification
novel
C2-symmetric
imidazolidine
carboxylic
acids
(CICAs),
which
are
easily
accessible
one-pot
fashion,
effective
ligands.
This
ruthenium/CICA
system
enabled
installation
central
axial
chirality,
featured
excellent
branched
linear
ratios
with
generally
>20
:
1
dr
up
98
2
er.
Mechanistic
studies
experiment
computation
were
carried
out
understand
catalyst
mode
action.
Chemical Science,
Год журнала:
2022,
Номер
13(14), С. 4088 - 4094
Опубликована: Янв. 1, 2022
Thioethers
allowed
for
highly
atroposelective
C-H
olefinations
by
a
palladium/chiral
phosphoric
acid
catalytic
system
under
ambient
air.
Both
N-C
and
C-C
axial
chiral
(hetero)biaryls
were
successfully
constructed,
leading
to
broad
range
of
axially
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.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(22), С. 11165 - 11206
Опубликована: Янв. 1, 2024
This
review
explores
the
fascinating
world
of
molecules
featuring
multiple
stereogenic
elements,
unraveling
different
strategies
designed
over
years
for
their
enantioselective
synthesis.
Organic Letters,
Год журнала:
2021,
Номер
23(19), С. 7401 - 7406
Опубликована: Сен. 17, 2021
Atropoisomeric
biaryl
motifs
are
widely
found
in
natural
products
and
bioactive
compounds
as
well
chiral
catalysts
ligands.
Various
efficient
approaches
have
been
disclosed
for
the
construction
of
six–six
skeletons.
In
contrast,
enantioselective
synthesis
axially
arylindoles
through
strategy
de
novo
construction,
other
than
asymmetric
functionalization
indoles,
remain
a
challenging
task.
Herein
we
report
an
Pd(0)/(S)-Segphos-catalyzed
atroposelective
Cacchi
reaction
2-alkynylanilines
with
sterically
congested
naphthyl
halides,
which
afforded
array
naphthyl-C3-indoles
high
yields
good
to
excellent
atroposelectivities.
The
addition
water
modulation
manipulation
procedure
by
premixing
palladium
complex
halide
were
keys
success.
conformational
stability
obtained
naphthyl-C3-indole
containing
synthetically
more-valuable
free
NH
moiety
is
revealed
kinetic
experiments.
ChemCatChem,
Год журнала:
2021,
Номер
13(16), С. 3547 - 3564
Опубликована: Июнь 7, 2021
Abstract
Pentatomic
heterobiaryl
performs
as
a
key
structural
motif
in
various
natural
products
and
bioactive
compounds.
With
the
rapid
growth
of
asymmetric
catalysis,
five‐membered
heterobiaryl‐based
catalysts
ligands
have
emerged
an
efficient
complementary
toolbox
for
catalysis.
Therefore,
development
enantioselective
construction
such
pentatomic
atropisomers
has
received
significant
attention
recent
decade.
Various
catalytic
strategies
been
established,
including
central
to
axial
chirality
conversion,
direct
generation
heteroaryl,
assembly
aryl‐heteroaryls,
functionalization
racemic
or
prochiral
biaryls,
transfer
from
atropisomeric
alkenes.
Hundreds
unprecedented
proliferated.
Importantly,
few
promising
axially
chiral
obtained
prepared
heterobiaryls
after
simple
transformations.
Hence,
advances
through
catalysis
are
summarized
this
review,
involving
their
scope,
mechanism,
transformations,
applications.
Organic Letters,
Год журнала:
2022,
Номер
24(20), С. 3620 - 3625
Опубликована: Май 16, 2022
The
Rh(III)-catalyzed
highly
enantioselective
C2-arylation
of
indole
derivatives
with
1-diazonaphthoquinones
is
reported.
In
the
presence
2.5
mol
%
SCpRh
complex
and
20
AgNO3,
reactions
indoles
proceeded
smoothly,
affording
a
wide
range
C2-arylated
atropisomers
in
good
yields
enantioselectivity
(≤96%
yield,
≤97%
ee)
under
mild
conditions.
method
displays
broad
substrate
scope
functional
group
tolerance.
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.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(8), С. 2109 - 2115
Опубликована: Янв. 1, 2022
An
enantioselective
olefinic
C–H
alkenylation
using
transient
group
was
disclosed
to
afford
axially
chiral
aryl
1,3-dienes
in
up
99%
yields
and
>99%
ee.
The
derived
carboxylic
acid
efficient
ligand
asymmetric
alkylation.
