Chemical Science,
Journal Year:
2017,
Volume and Issue:
8(9), P. 6645 - 6649
Published: Jan. 1, 2017
An
enantioselective
hydroxylative
dearomatization
of
2-naphthols
with
oxaziridines
has
been
accomplished
using
a
N,N'-dioxide-scandium(iii)
complex
catalyst.
Various
substituted
ortho-quinols
could
be
obtained
in
high
yields
(up
to
99%)
and
enantioselectivities
95
:
5
er).
This
methodology
applied
the
synthesis
bioactive
lacinilenes
gram-scale
reaction.
Based
on
experimental
investigations
previous
work,
possible
catalytic
model
was
proposed.
Angewandte Chemie International Edition,
Journal Year:
2017,
Volume and Issue:
56(12), P. 3237 - 3241
Published: Jan. 9, 2017
Abstract
An
Ir‐catalyzed
intermolecular
asymmetric
dearomatization
reaction
of
β‐naphthols
with
allyl
alcohols
or
ethers
was
developed.
When
an
iridium
catalyst
generated
from
[Ir(COD)Cl]
2
(COD=cyclooctadiene)
and
a
chiral
P/olefin
ligand
is
employed,
highly
functionalized
β‐naphthalenone
compounds
bearing
all‐carbon‐substituted
quaternary
center
were
obtained
in
up
to
92
%
yield
98
ee
.
The
direct
utilization
as
electrophiles
represents
improvement
the
viewpoint
atom
economy.
Allyl
found
undergo
allylic
substitution
under
Ir
catalysis
for
first
time.
diverse
transformations
dearomatized
product
various
motifs
render
this
method
attractive.
European Journal of Organic Chemistry,
Journal Year:
2020,
Volume and Issue:
2020(27), P. 4087 - 4097
Published: Feb. 19, 2020
The
catalytic
dearomatization
of
naphthols
offers
a
unique
platform
to
rapidly
access
structurally
complex
and
densely
functionalized
molecular
architectures.
Thermodynamically
more
favorable,
with
respect
the
analogous
phenol‐variant,
transformation
phenolic
ring
into
corresponding
naphthalenone
(cited
here
as
naphthyl
dearomatization)
has
faced
considerable
amount
attention
over
past
decade
constant
improvements
towards
stereocontrol.
A
collection
most
representative
recent
variants
involving
carbon–carbon
well
carbon–heteroatom
bond
forming
events
are
presented
in
this
Minireview
article.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(12), P. 9244 - 9253
Published: June 3, 2024
Catalytic
asymmetric
dearomatization
(CADA)
is
a
powerful
tool
for
the
rapid
construction
of
complex
chiral
three-dimensional
cyclic
molecules
featuring
quaternary
carbon
centers
from
readily
available
arenes.
However,
ubiquitous
nonfunctionalized
1-naphthols
to
afford
remains
challenging
and
undeveloped.
This
study
reports
dearomative
[4
+
1]
spiroannulation
via
copper
catalysis.
reaction
features
highly
chemo-,
regio-,
stereoselective
nucleophilic
addition
intramolecular
annulation
cascade
reactive
π-extended
copper-allenylidene,
thus
enabling
practical
synthesis
range
valuable
spirocyclic
enones
bearing
stereocenter
with
high
efficiency.
Furthermore,
this
protocol
applicable
phenols.
Control
experiments
supported
substitution-annulation
mechanism
by
excluding
process
involving
1,3-sigmatropic
shift.
Preliminary
biological
activity
studies
indicated
that
synthesized
hold
significant
promise
as
anticancer
agents
inducing
tumor
cell
apoptosis.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(12), P. 9254 - 9264
Published: June 3, 2024
Catalytic
asymmetric
dearomatization
reactions
of
α-unsubstituted
β-naphthols
are
very
challenging
due
to
the
high
energy
barrier
resulting
from
loss
aromaticity.
Herein,
we
describe
an
example
enantioselective
catalytic
dearomative
spiroannulation
with
yne-allylic
esters.
The
success
this
reaction
relied
on
copper-catalyzed
remote
strategy
using
esters
as
bis-electrophilic
reagents.
This
transformation
features
mild
conditions,
broad
functional
group
tolerance,
and
extensive
substrate
scope,
thereby
facilitating
efficient
construction
array
enantioenriched
naphthalene-2-one
spiroindolenine
derivatives.
Experimental
studies
density
theory
calculations
establish
pathway
origin
stereoselectivity.
Journal of the American Chemical Society,
Journal Year:
2017,
Volume and Issue:
140(2), P. 735 - 740
Published: Dec. 18, 2017
Direct
aerobic
α,β-dehydrogenation
of
γ,δ-unsaturated
amides
and
acids
using
a
simple
iridium/copper
relay
catalysis
system
is
described.
We
developed
new
strategy
that
overcomes
the
challenging
issue
associated
with
low
α-acidity
acids.
Instead
α-C–H
metalation,
this
reaction
proceeds
by
β-C–H
activation,
which
results
in
enhanced
α-acidity.
Conjugated
dienamides
dienoic
were
synthesized
excellent
yield
reaction,
uses
protocol.
Mechanistic
experiments
suggest
catalyst
resting
state
mechanism
both
cleavage
accelerated.
Organic Chemistry Frontiers,
Journal Year:
2016,
Volume and Issue:
3(6), P. 759 - 763
Published: Jan. 1, 2016
A
series
of
novel
chiral
monophosphine
ligands
Xiang-Phoses
were
designed
and
have
been
applied
to
the
enantioselective
gold-catalyzed
intermolecular
[2
+
2]-cycloaddition
3-styrylindoles
1
with
N-allenyl
oxazolidinone
2.
Angewandte Chemie International Edition,
Journal Year:
2016,
Volume and Issue:
55(28), P. 8113 - 8116
Published: May 10, 2016
A
chiral
iridium(I)
N-heterocyclic
carbene
complex
was
reported
for
the
first
time
as
catalyst
in
highly
enantioselective
intramolecular
allylic
amination
reaction.
The
current
method
provides
facile
access
to
biologically
important
enantioenriched
indolopiperazinones
and
piperazinones
good
yields
(74-91
%)
excellent
enantioselectivities
(92-99
%
ee).
Preliminary
mechanistic
investigations
reveal
that
C-H
activation
occurs
at
position
ortho
N-aryl
group
of
ligand.
Chemical Communications,
Journal Year:
2020,
Volume and Issue:
57(10), P. 1262 - 1265
Published: Dec. 22, 2020
A
palladium-catalyzed
allylic
alkylation
dearomatization
of
β-naphthols
and
indoles
withgem-difluorinated
cyclopropanes
has
been
developed
for
the
first
time.
Angewandte Chemie International Edition,
Journal Year:
2016,
Volume and Issue:
55(51), P. 15910 - 15914
Published: Nov. 23, 2016
Abstract
A
dearomative
reduction
of
simple
arenes
has
been
developed
which
employs
a
visible‐light‐mediated
cycloaddition
with
an
N‐N‐arenophile
and
in
situ
diimide
reduction.
Subsequent
cycloreversion
or
fragmentation
the
arenophile
moiety
affords
1,3‐cyclohexadienes
1,4‐diaminocyclohex‐2‐enes,
compounds
that
are
not
synthetically
accessible
using
existing
dearomatization
reactions.
Importantly,
this
strategy
also
provides
numerous
opportunities
for
further
derivatization
as
well
site‐selective
functionalization
polynuclear
arenes.
