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.
Asian Journal of Organic Chemistry,
Год журнала:
2022,
Номер
11(10)
Опубликована: Авг. 3, 2022
Abstract
Polycyclic
fused
indoline
derivatives,
specifically
those
bearing
tertiary
or
quaternary
carbon
stereocenters
at
C2
and
C3
positions,
stand
as
an
important
class
of
nitrogen‐containing
heterocyclic
compounds
because
they
are
frequently
occurring
core
structures
in
a
wide
variety
alkaloid
natural
products,
pharmaceutical
molecules,
functional
materials.
Over
the
past
few
decades,
development
new
versatile
synthetic
approaches
for
construction
indolines
has
been
focus
great
deal
research
initiatives.
In
this
review,
recent
advances
dearomative
annulation
N‐
acylindoles
with
diverse
nucleophiles
summarized
since
2012,
which
could
be
divided
into
five
categories:
1)
Dearomative
Heck
reactions
acylindoles;
2)
Visible‐light‐induced
reductive
dearomatization
3)
Lewis
acid‐catalyzed
4)
Asymmetric
5)
by
other
closely
related
reagents.
Nature Chemistry,
Год журнала:
2023,
Номер
15(4), С. 560 - 568
Опубликована: Март 9, 2023
Ribosomally
synthesized
and
post-translationally
modified
peptide
natural
products
have
provided
many
highly
unusual
scaffolds.
This
includes
the
intriguing
alkaloids
crocagins,
which
possess
a
tetracyclic
core
structure
whose
biosynthesis
has
remained
enigmatic.
Here
we
use
in
vitro
experiments
to
demonstrate
that
three
proteins,
CgnB,
CgnC
CgnE,
are
sufficient
for
production
of
hallmark
crocagin
from
precursor
CgnA.
The
crystal
structures
homologues
CgnB
CgnE
reveal
them
be
founding
members
peptide-binding
protein
family
allow
us
rationalize
their
distinct
functions.
We
further
show
hydrolase
CgnD
liberates
scaffold,
is
subsequently
N-methylated
by
CgnL.
These
insights
propose
biosynthetic
scheme
crocagins.
Bioinformatic
analyses
based
on
these
data
led
discovery
related
pathways
may
provide
access
structurally
diverse
peptide-derived
pyrroloindoline
alkaloids.
ACS Catalysis,
Год журнала:
2024,
Номер
14(8), С. 5605 - 5611
Опубликована: Март 29, 2024
The
development
of
benzylic
C(sp3)–H
functionalization
methods
for
the
assembly
derivatives
has
been
extensively
explored
in
recent
years.
However,
engagement
carbon
and
its
adjacent
C=C
bond
as
a
C3
synthon
cycloaddition
reaction
via
direct
C–H
activation
is
rare.
Herein,
we
report
copper-catalyzed
[3+3]
radical
through
to
construct
six-membered
cyclohexane-type
rings.
In
this
reaction,
2-benzylic
an
indole
selectively
activated
serves
that
reacts
highly
chemoselective
intermolecular
self-[3+3]
cross-[3+3]
pathways.
Multiple
symmetric
nonsymmetric
polycyclic
hexahydrocarbazole
scaffolds
with
hexacyclic
6/5/5/6/5/5/6
pentacyclic
6/5/5/6/5/6
ring
systems
are
synthesized
high
efficiency
chemoselectivity
using
strategy.
Inspired
by
unique
addition
pathway
cycloaddition,
controllable
construction
C3a-alkylated
pyrroloindolines
was
also
developed.
Organic Letters,
Год журнала:
2024,
Номер
26(23), С. 4932 - 4937
Опубликована: Июнь 3, 2024
Herein
we
report
the
first
use
of
p-quinone
diimide
for
aminative
dearomatization
2,3-disubstituted
indoles
to
furnish
C3
aza-quaternary
chiral
indolenines.
This
approach,
which
proceeds
via
an
electrophilic
1,6-addition
diimide,
allows
synthesis
array
optically
active
indolenines
with
high
yields
and
excellent
enantioselectivities.
A
one-pot
approach
same
has
also
been
established
further
improve
synthetic
accessibility
this
protocol.
ACS Catalysis,
Год журнала:
2021,
Номер
12(2), С. 837 - 845
Опубликована: Дек. 29, 2021
A
1,2-difunctionalization
of
an
unactivated
alkene,
imidoyl-carbamoylation,
has
been
developed
through
a
palladium-catalyzed
four-component
cascade
reaction
involving
aryl
iodide,
alkenyl
isocyanide,
CO,
and
amine.
Continuous
migratory
insertion
three
different
functionalities
to
the
Pd(II)
intermediate
generated
from
previous
step
takes
place
in
well-defined
sequence.
Four
chemical
bonds,
including
C–C
bonds
one
C–N
bond,
are
formed
this
process,
leading
convenient
convergent
access
acetamides
substituted
with
five-
seven-membered
cyclic
ketoimines.
In
addition,
extra
bond
is
situ
or
postreaction
cyclization
amido
NH
ketoimine
moiety,
providing
facile
one-pot
pyrrolo-fused
heterocycles.
Abstract
Herein,
the
first
diversity‐oriented
catalytic
asymmetric
dearomatization
of
indoles
with
o
‐quinone
diimides
(
‐QDIs)
is
reported.
The
(CADA)
one
research
focuses
in
terms
structural
and
biological
importance
dearomatized
indole
derivatives.
Although
great
achievements
have
been
made
target‐oriented
CADA
reactions,
reactions
are
regarded
as
more
challenging
remain
elusive
due
to
lack
synthons
featuring
multiple
reaction
sites
difficulty
precise
control
chemo‐,
regio‐,
enantio‐selectivity.
In
this
work,
‐QDIs
employed
a
versatile
building
block,
enabling
chemo‐divergent
dearomative
arylation
[4
+
2]
cycloaddition
indoles.
Under
catalysis
chiral
phosphoric
acid
mild
conditions,
various
indolenines,
furoindolines/pyrroloindolines,
six‐membered‐ring
fused
indolines
collectively
prepared
good
yields
excellent
enantioselectivities.
This
synthesis
protocol
enriches
chemistry
offers
new
opportunities
for
reactions.
Organic Letters,
Год журнала:
2023,
Номер
25(33), С. 6122 - 6127
Опубликована: Авг. 14, 2023
Herein,
we
describe
a
nickel-catalyzed
asymmetric
dearomative
aryl-difluoroallylation
reaction
of
indoles
with
α-trifluoromethyl
alkenes
as
an
electrophilic
coupling
partner.
The
proceeds
via
cascade
sequence
involving
Heck
cyclization
and
reductive
allylic
defluorination.
A
series
gem-difluoroallyl
substituted
indolines
are
obtained
in
moderate
to
good
yields
(36-77%
yield)
excellent
enantioselectivity
(up
99%
ee).
features
broad
functional
group
tolerance,
scaled-up
synthesis,
late-stage
diversification.
