The Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
87(9), P. 6025 - 6037
Published: April 18, 2022
A
dearomatization
process
of
3-nitroindoles
enabled
using
palladium-catalyzed
decarboxylative
[4
+
2]
cycloaddition
either
2-alkylidenetrimethylene
carbonates
or
2-(hydroxymethyl)-3-arylallyl
has
been
developed,
affording
a
wide
range
indoline-fused
tetrahydropyrans
in
good
yields
with
excellent
diastereoselectivities.
This
reaction
features
substrate
scope
and
mild
conditions
represents
the
first
example
application
π-allyl
palladium
1,4-[O,C]-dipole
species
for
dearomative
electron-deficient
heteroarenes.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
59(2), P. 648 - 652
Published: Oct. 8, 2019
Abstract
The
enantioselective
dearomatization
of
indoles
by
an
organocatalytic
(3+2)
reaction
has
been
established.
makes
use
simple
indole
derivatives
as
substrates,
and
employs
azoalkenes
partners.
A
wide
range
pyrroloindolines
containing
all‐carbon
quaternary
stereogenic
center
were
readily
prepared
in
high
yields
with
excellent
enantioselectivities.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(33), P. 13441 - 13449
Published: Aug. 16, 2021
Visible-light-induced
cycloaddition
reactions
initiated
via
energy-transfer
processes
have
recently
evolved
as
powerful
methods
for
the
construction
of
strained
cyclic
molecules
that
are
not
easily
accessed
using
known
ground-state
synthetic
methods.
Particularly,
by
excitation
aromatic
rings
provide
an
alternative
solution
to
direct
transformations
feedstocks
under
scheme
dearomatization.
Vinylcyclopropanes
(VCPs)
well-known
reagents
in
radical
clock
experiments,
working
a
probe
detect
transient
intermediates.
However,
applications
this
regard
still
remain
limited
due
uncontrollable
selectivities.
Herein,
we
report
visible-light-induced
dearomatization
indole-
or
pyrrole-tethered
VCPs,
which
several
competitive
reaction
pathways,
including
[5
+
2],
[2
interrupted
and
4]
cycloadditions,
can
be
well
regulated
engineering
substrate
structures
tuning
conditions.
The
mechanism
has
been
explored
combined
experimental
computational
investigations.
These
convenient
method
synthesize
structurally
diverse
polycyclic
with
high
efficiency
good
selectivity.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
53(2), P. 883 - 971
Published: Dec. 18, 2023
This
review
aims
to
collect
advancements
in
enantioselective
palladium-catalyzed
cyclization
reactions
over
the
past
eleven
years,
and
it
is
organized
into
thirteen
sections
depending
on
different
types
of
transformations
involved.
Organic Letters,
Journal Year:
2018,
Volume and Issue:
20(10), P. 2880 - 2883
Published: May 7, 2018
A
palladium-catalyzed
enantioselective
[4
+
2]
cycloaddition
reaction
of
vinyl
benzoxazinones
with
sulfamate-derived
cyclic
imines
is
described,
affording
the
tetrahydroquinazolines
bearing
several
functional
rings
in
high
yields
(up
to
99%
yield)
good
excellent
diastereoselectivities
and
enantioselectivities
96%
ee).
This
represents
first
Pd-catalyzed
asymmetric
decarboxylative
imines.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(49), P. 17211 - 17217
Published: Nov. 13, 2018
The
first
Lewis
acid
catalyzed
stereoconvergent
transformation
of
racemic
2-(hetero)aryl-N-sulfonylaziridines
via
C–N
bond
cleavage
with
nucleophiles
is
presented.
This
includes
the
[3
+
2]
annulations
(hetero)aromatic
aldehydes
and
1,3-disubstituted
indoles,
asymmetric
Friedel–Crafts
type
reaction
electron-rich
(hetero)arenes,
aminolysis
amines,
providing
facile
access
to
chiral
1,3-isoxazolidines,
pyrroloindolines,
2-(hetero)arylphenethylamines,
vicinal
diamines.
method
features
a
simple
cheaply
available
complex
Cu(I)–chiral
BINAP
catalyst,
excellent
yield
high
diastereo-
enantioselectivities,
mild
conditions.
A
mechanism
involving
I
dynamic
kinetic
transformations
(DyKATs)
aziridines
proposed
based
on
results
control
experiments.
The Journal of Organic Chemistry,
Journal Year:
2019,
Volume and Issue:
84(7), P. 4381 - 4391
Published: March 13, 2019
An
organocatalyzed
dearomative
aza-Michael/Michael
addition
cascade
of
2-nitrobenzofurans
and
2-nitrobenzothiophenes
with
2-aminochalcones
has
been
developed,
opening
a
new
channel
to
access
series
optically
active
tetrahydrobenzofuro[3,2-b]quinolines
tetrahydrobenzo[4,5]thieno[3,2-b]quinolines
bearing
three
contiguous
stereocenters
excellent
diastereo-
enantioselectivities
(all
cases
>20:1
dr,
up
99%
ee).
This
study
features
the
first
asymmetric
reaction
beginning
aza-Michael
addition.
The
potential
applications
methodology
were
demonstrated
by
preparative-scale
experiment
versatile
transformations
products.
Chemical Communications,
Journal Year:
2020,
Volume and Issue:
57(1), P. 27 - 44
Published: Nov. 25, 2020
3-Nitroindoles
behave
as
electron-poor
aromatic
compounds
and
react
toward
a
number
electron-rich
species.
This
feature
article
presents
an
overview
of
this
reactivity,
mainly
in
(formal)
dearomatizing
cycloaddition
reactions.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(43), P. 19932 - 19941
Published: Oct. 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.
