Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
135(8)
Published: Dec. 27, 2022
Abstract
Herein,
an
I
2
‐catalyzed
unprecedented
cycloisomerization
of
ynamides
is
developed,
furnishing
various
functionalized
bis(indole)
derivatives
in
generally
good
to
excellent
yields
with
wide
substrate
scope
and
atom‐economy.
This
protocol
not
only
represents
the
first
molecular‐iodine‐catalyzed
tandem
complex
alkyne
cycloisomerizations,
but
also
constitutes
chemoselective
tryptamine‐ynamides
involving
distinctively
different
C(sp
3
)−C(sp
)
bond
cleavage
rearrangement.
Moreover,
chiral
tetrahydropyridine
frameworks
containing
two
stereocenters
are
obtained
moderate
diastereoselectivities
enantioselectivities.
Meanwhile,
aromatization
produce
pyrrolyl
indoles
high
efficiency
enabled
by
.
Additionally,
control
experiments
theoretical
calculations
reveal
that
this
reaction
probably
undergoes
a
5‐exo‐dig
cyclization/rearrangement
process.
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
57(37), P. 12121 - 12125
Published: July 14, 2018
Abstract
A
highly
enantio‐
and
diastereoselective
formal
(4+3)
cycloaddition
of
1,3‐diene‐1‐carbamates
with
3‐indolylmethanols
in
the
presence
a
chiral
phosphoric
acid
catalyst
is
reported.
The
approach
described
herein
provides
efficient
access
to
6‐aminotetrahydrocyclohepta[b]indoles
good
yields
mostly
complete
diastereoselectivity
excellent
levels
enantioselectivity
(>98:2
dr
up
98
%
ee).
Mild
reaction
conditions,
facile
scale‐up,
versatile
derivatization
highlight
practicality
this
methodology.
mechanistic
study
suggests
that
occurs
stepwise
fashion,
after
formation
an
ion
pair
between
catalytic
phosphate
intermediate
carbocation.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(49), P. 21991 - 21996
Published: Sept. 2, 2020
Abstract
A
palladium‐catalyzed
intermolecular
dynamic
kinetic
asymmetric
dearomatization
of
3‐arylindoles
with
internal
alkynes
was
developed
the
use
achiral
Xantphos
and
chiral
sulfinamide
phosphine
ligand
(
PC‐Phos
)
as
co‐ligands.
This
method
could
deliver
various
spiro[indene‐1,3′‐indole]
compounds
in
good
yields
(up
to
95
%
yield)
up
98
ee
.
The
salient
features
transformation
include
readily
available
substrates,
ease
scale‐up
versatile
functionalization
products.
mechanistic
experiments
gave
some
insights
on
active
intermediates.
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
58(1), P. 216 - 220
Published: Nov. 13, 2018
Abstract
An
organocatalytic
one‐step
desymmetrizing
dearomatization
reaction
of
indoles
with
in
situ
formed
vinylidene
ortho
‐quinone
methides
is
reported.
A
set
[6‐6‐5]
and/or
[5‐6‐5]
fused
indoline
heterocycles
were
obtained
excellent
yields
diastereoselectivities
(>20:1
d.r.)
and
enantioselectivities
(up
to
99
%
ee
).
Moreover,
some
the
products
screened
against
a
panel
cancer
cell
lines,
one
was
identified
inhibit
proliferation
all
tested
cells,
but
showed
marginal
effects
non‐cancerous
cells.
The
methodology
provides
platform
for
synthesis
new
leading
compounds
antitumor
activity.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(30), P. 10245 - 10249
Published: May 15, 2019
A
protocol
for
palladium-catalyzed
dearomative
functionalization
of
simple,
nonactivated
arenes
with
Grignard
reagents
has
been
established.
This
one-pot
method
features
a
visible-light-mediated
[4+2]
cycloaddition
between
an
arene
and
arenophile,
subsequent
allylic
substitution
the
resulting
cycloadduct
reagent.
variety
can
participate
in
this
process,
forming
carboaminated
products
exclusive
syn-1,4-selectivity.
Moreover,
dearomatized
are
amenable
to
further
elaborations,
providing
functionalized
alicyclic
motifs
pharmacophores.
For
example,
naphthalene
was
converted
into
sertraline,
one
most
prescribed
antidepressants,
only
four
operations.
Finally,
process
could
also
be
conducted
enantioselective
fashion,
as
demonstrated
desymmetrization
naphthalene.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(4)
Published: Nov. 26, 2022
The
construction
of
allylic
quaternary
sp3
-carbon
centers
has
long
been
a
formidable
challenge
in
transition-metal-catalyzed
alkyl-allyl
coupling
reactions
due
to
the
severe
steric
hindrance.
Herein,
we
report
an
effective
carbene
strategy
that
employs
well-defined
vinyl-N-triftosylhydrazones
as
versatile
allylating
reagent
enable
direct
assembly
these
medicinally
desirable
structural
elements
from
low-cost
alkane
feedstocks.
reaction
exhibited
excellent
site
selectivity
for
tertiary
C-H
bonds,
broad
scope
(>60
examples
and
>20
:
1:0
r.
r.)
good
efficiency,
even
on
gram-scale,
making
it
convenient
alternative
well-known
Trost-Tsuji
allylation
formation
bonds.
Combined
experimental
computational
studies
were
employed
unravel
mechanism
origin
site-
chemoselectivity
reaction.
Chemistry - A European Journal,
Journal Year:
2019,
Volume and Issue:
25(17), P. 4330 - 4334
Published: Jan. 29, 2019
Abstract
An
intermolecular
asymmetric
cascade
dearomatization
reaction
of
indole
derivatives
with
propargyl
carbonate
was
developed.
The
challenges
associated
both
the
chemoselectivity
between
carbon
and
nitrogen
nucleophile
enantioselective
control
during
formation
an
all‐carbon
quaternary
stereogenic
center
were
well
addressed
by
a
Pd
catalytic
system
derived
from
Feringa
ligand.
A
series
enantioenriched
multiply
substituted
fused
indolenines
provided
in
good
yields
(71–86
%)
excellent
enantioselectivity
(91–96
%
ee
)
(
3
/
4
>19:1
most
cases).
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
57(49), P. 16190 - 16193
Published: Oct. 17, 2018
Abstract
Guided
by
the
mechanistic
insights
from
computational
studies,
we
have
developed
an
Ir‐catalyzed
asymmetric
intramolecular
allylic
dearomatization
reaction
of
benzene
derivatives.
Under
optimized
conditions
consisting
a
readily
available
Ir
catalyst,
series
spiro[4.5]cyclohexadiene
compounds
were
delivered
in
reasonable
yields
(up
to
79
%)
with
good
enantioselectivity
99
%
ee
).
The
introduction
malonate
diester‐type
substituent
serves
as
key
strategy
guide
nucleophilic
reactivity
ring.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(9), P. 3788 - 3792
Published: April 26, 2021
Herein,
we
report
a
highly
enantio-
and
diastereoselective
rhodium-catalyzed
cyclization
of
N-allenyltryptamines
3-allenylindoles
to
6-membered
spirocyclic
indolenines.
This
allylic
addition
methodology
offers
the
advantage
using
comparably
cheap
commercially
available
ligand
with
low
loadings
an
affordable
rhodium
precursor.
The
products
can
be
converted
into
functionalized
spirooxindoles
spiroindolines,
which
are
regarded
as
important
building
blocks
for
synthesis
lot
natural
biological
activities.
Chemistry - A European Journal,
Journal Year:
2018,
Volume and Issue:
25(10), P. 2442 - 2446
Published: Dec. 3, 2018
Abstract
A
metal‐free,
phosphine‐catalyzed
intramolecular
“umpolung
Michael
addition”
on
alkynes
to
form
spiroindol(en)ines
is
reported.
This
nucleophilic
catalysis
enables
the
formation
of
a
wide
scope
five‐
and
six‐membered
in
moderate
excellent
yields
batch
as
well
under
continuous‐flow
conditions.
Triphenylphosphine‐catalyzed
activation
allows
exclusive
exo
‐product
mild
reaction
Angewandte Chemie,
Journal Year:
2020,
Volume and Issue:
132(49), P. 22175 - 22180
Published: Sept. 2, 2020
Abstract
A
palladium‐catalyzed
intermolecular
dynamic
kinetic
asymmetric
dearomatization
of
3‐arylindoles
with
internal
alkynes
was
developed
the
use
achiral
Xantphos
and
chiral
sulfinamide
phosphine
ligand
(
PC‐Phos
)
as
co‐ligands.
This
method
could
deliver
various
spiro[indene‐1,3′‐indole]
compounds
in
good
yields
(up
to
95
%
yield)
up
98
ee
.
The
salient
features
transformation
include
readily
available
substrates,
ease
scale‐up
versatile
functionalization
products.
mechanistic
experiments
gave
some
insights
on
active
intermediates.
