The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(11), С. 7552 - 7560
Опубликована: Май 28, 2024
Herein,
a
palladium-catalyzed
diastereoselective
dearomatization/cross-coupling
cyclization
reaction
between
N-arylacyl
indoles
and
(E)-β-chlorovinyl
ketones
is
reported.
Through
this
cyclization/cycloisomerization
cascade,
series
of
furan-containing
indolines
were
obtained
in
yields
up
to
95%.
The
features
readily
accessible
starting
materials,
benzyl
Pd(II)-catalyzed
cycloisomerization
ketones,
the
sequential
formation
three
bonds
bis-heterocycles,
excellent
diastereoselectivity.
More
importantly,
carbene–secondary
migratory
insertion
proven
be
critical
process
cyclizations.
Natural Product Reports,
Год журнала:
2022,
Номер
39(9), С. 1721 - 1765
Опубликована: Янв. 1, 2022
Covering:
up
to
2022Pyrroloindoline
is
a
privileged
tricyclic
indoline
motif
widely
present
in
many
biologically
active
and
medicinally
valuable
natural
products.
Thus,
understanding
the
biosynthesis
of
this
molecule
critical
for
developing
convenient
synthetic
routes,
which
highly
challenging
its
chemical
synthesis
due
presence
rich
chiral
centers
molecule,
especially
fully
substituted
carbon
center
at
C3-position
rigid
structure.
In
recent
years,
progress
has
been
made
elucidating
biosynthetic
pathways
enzymatic
mechanisms
pyrroloindoline-containing
products
(PiNPs).
This
article
reviews
main
advances
past
few
decades
based
on
different
substitutions
C3
position
PiNPs,
various
key
involved
types
PiNPs.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(6), С. 1521 - 1526
Опубликована: Янв. 1, 2023
A
highly
efficient
[4
+
1]
annulation
of
sulfur
ylide
salts
and
o
-sulfonamido
aldimines
for
construction
valuable
2,3-disubstituted
indolines
is
reported.
It
worth
noting
that
indoles
could
also
be
synthesized
by
this
cascade
reaction.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Фев. 16, 2024
Abstract
Small
molecules
with
conformationally
rigid,
three-dimensional
geometry
are
highly
desirable
in
drug
development,
toward
which
a
direct,
simple-to-complexity
synthetic
logic
is
still
of
considerable
challenges.
Here,
we
report
intermolecular
aza-[2
+
2]
photocycloaddition
(the
aza-Paternò–Büchi
reaction)
indole
that
facilely
assembles
planar
building
blocks
into
ladder-shape
azetidine-fused
indoline
pentacycles
contiguous
quaternary
carbons,
divergent
head-to-head/head-to-tail
regioselectivity,
and
absolute
exo
stereoselectivity.
These
products
exhibit
marked
three-dimensionality,
many
possess
3D
score
values
distributed
the
highest
0.5%
region
reference
to
structures
from
DrugBank
database.
Mechanistic
studies
elucidated
origin
observed
regio-
stereoselectivities,
arise
distortion-controlled
C-N
coupling
scenarios.
This
study
expands
repertoire
energy
transfer
catalysis
for
accessing
structurally
intriguing
architectures
high
molecular
complexity
underexplored
topological
chemical
space.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(36)
Опубликована: Июнь 21, 2022
Abstract
Axially
chiral
biaryl
diols
have
achieved
great
success
in
asymmetric
catalysis.
By
contrast,
axially
amino
alcohols
are
far
less
developed.
Herein,
we
rationally
designed
a
versatile
C
1
‐symmetric
alcohol
scaffold
1‐(1‐amino‐pyrrol‐2‐yl)naphthalen‐2‐ol
(NPNOL)
on
the
basis
of
C2‐arylpyrrole
framework.
For
its
enantioselective
synthesis,
phosphoric
acid‐catalyzed
Attanasi
reaction
between
1,3‐dicarbonyl
compounds
and
azoalkenes
had
been
established.
using
this
practical
method,
wide
range
NPNOLs
were
readily
prepared
high
yields
excellent
atroposelectivities
(38
examples,
up
to
89
%
yield
99
ee
).
DFT
calculations
performed
reveal
mechanism
origins
enantioselectivity.
The
easy
transformations
NPNOL‐derived
products
into
organocatalysts/ligands
their
preliminary
applications
catalytic
reactions
demonstrated
promising
utility
NPNOL.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(43), С. 19932 - 19941
Опубликована: Окт. 21, 2022
Searching
for
efficient
strategies
to
access
structurally
novel
aminoindolines
is
of
great
significance
drug
discovery.
However,
catalytic
asymmetric
de
novo
construction
aminoindoline
scaffolds
with
functionality
primed
diversification
still
remains
elusive.
Here,
we
report
a
Cu-catalyzed
cyclization
ethynyl
benzoxazinones
amines,
producing
chiral
3-aminoindolines
in
good
yield
and
high
enantioselectivity
(up
97%
98:2
er).
Moreover,
radical-mediated
sulfonyl
migration
these
products
was
unexpectedly
found,
further
affording
new
bearing
alkenyl
groups
retained
enantiopurity
84%
Bioactivity
evaluations
indicate
that
show
notable
antitumor
activities
chirality
proven
have
significant
impact
on
their
activity.
The Chemical Record,
Год журнала:
2023,
Номер
23(3)
Опубликована: Фев. 1, 2023
Abstract
Indoles
and
their
derivatives
have
dominated
a
significant
proportion
of
nitrogen‐containing
heterocyclic
compounds
play
an
essential
role
in
synthetic
medicinal
chemistry,
pesticides,
advanced
materials.
Compared
with
conventional
strategies,
direct
functionalization
indoles
provides
straightforward
access
to
construct
diverse
indole
scaffolds.
As
we
enter
era
emphasizing
green
sustainable
utilizing
environment‐friendly
solvents
represented
by
water
demonstrates
great
potential
synthesizing
valuable
derivatives.
This
review
aims
depict
the
critical
aspects
aqueous‐mediated
over
past
decade
discusses
future
challenges
prospects
this
fast‐growing
field.
For
convenience
readers,
is
classified
into
three
parts
according
bonding
modes
(C−C,
C−N,
C−S
bonds),
which
focus
on
diversity
derivatives,
prominent
chemical
process,
types
catalyst
systems
mechanisms.
We
hope
can
promote
development
discovery
novel
practical
organic
methods
aqueous
phase.
Journal of Heterocyclic Chemistry,
Год журнала:
2024,
Номер
61(3), С. 528 - 537
Опубликована: Янв. 16, 2024
Abstract
A
dearomative
[4
+
2]
cycloaddition
of
3‐nitroindoles
ortho
‐amino
Morita−Baylis−Hillman
carbonates
was
established
under
mild
conditions.
This
method
provides
an
efficient
and
practical
approach
for
delivering
tetrahydro‐5
H
‐indolo[2,3‐
b
]quinolines
containing
three
contiguous
stereocenters,
two
tertiary
one
quaternary,
in
high
yield
(up
to
95%)
with
excellent
diastereoselectivity
(all
cases
>25:1
dr
).
The
potential
synthetic
applications
this
strategy
were
also
highlighted
by
the
scale‐up
experiment
further
transformation.
Moreover,
structure
relative
configuration
cycloadduct
unequivocally
confirmed
single‐crystal
X‐ray
diffraction.
Organic Letters,
Год журнала:
2024,
Номер
26(15), С. 3310 - 3315
Опубликована: Апрель 8, 2024
A
catalyst
system
consisting
of
a
chiral
phosphoramidite
ligand
and
Pd2(dba)3·CHCl3
causes
the
decarboxylation
5-vinyloxazolidine-2,4-diones
to
generate
amide-containing
aza-π-allylpalladium
1,3-dipole
intermediates,
which
are
capable
triggering
dearomatization
3-nitroindoles
for
diastereo-
enantioselective
[3+2]
cycloaddition,
leading
formation
series
highly
functionalized
pyrroloindolines
containing
three
contiguous
stereogenic
centers
with
excellent
results
(up
99%
yield,
88:12
dr,
96%
ee).
Chemical Communications,
Год журнала:
2024,
Номер
60(53), С. 6773 - 6776
Опубликована: Янв. 1, 2024
A
novel
phosphine-mediated
α-umpolung/Wittig
olefination/cyclization
cascade
process
between
o
-aminobenzaldehydes
and
Morita–Baylis–Hillman
(MBH)
carbonates
has
been
ingeniously
developed
for
the
facile
synthesis
of
a
broad
range
2-vinylindolines.
We
report
the
first
example
of
dearomative
(3
+
2)
cycloadditions
3-nitro(aza)-indole,
-benzofuran,
and
-benzothiophene
derivatives
in
presence
allenyl
sulfones,
using
sulfinate
ammonium
ion
pairs
as
organocatalytic
promoters.
The
methodology
provides
a
new,
facile,
efficient
protocol
for
synthesis
functionalized
2,3-fused
cyclopentannulated
indolines
dihydrobenzofurans.
