Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(69)
Published: Sept. 14, 2023
We
disclose
a
catalytic,
enantioselective
dearomative
reaction
of
non-functionalized
1-naphthols,
which
poses
synthetic
challenge
to
organic
chemists
because
the
relative
ease
rearomatization
via
elimination
proton.
In
this
work,
direct
dearomatization
1-naphthols
was
achieved
through
chiral
phosphoric
acid
(CPA)
catalyzed
[4+2]
cycloaddition
with
in-situ
generated
ortho-quinone
methides
(o-QMs).
The
reported
convergent
method
allows
use
readily
available
simple
without
pre-functionalization,
furnishing
variety
naphthopyran
derivatives
in
good
yields
(up
96
%)
and
moderate
excellent
enantioselectivities
>99
%
ee)
under
mild
conditions.
observed
regio-,
diastereo-,
are
keys
success
current
strategy
utilizing
o-QM
as
diene
surrogates,
combination
CPA
catalysis.
Organic Chemistry Frontiers,
Journal Year:
2020,
Volume and Issue:
7(23), P. 3967 - 3998
Published: Jan. 1, 2020
This
review
summarizes
the
progresses
in
organocatalytic
asymmetric
dearomatization
reactions
of
indole
derivatives
and
their
applications
total
synthesis
natural
products,
gives
some
insights
into
challenging
issues
this
research
field.
Organic & Biomolecular Chemistry,
Journal Year:
2021,
Volume and Issue:
19(18), P. 3960 - 3982
Published: Jan. 1, 2021
Bridged
polycycles
are
privileged
molecular
skeletons
with
wide
occurrence
in
bioactive
natural
products
and
pharmaceuticals.
Therefore,
they
have
been
the
pursing
target
molecules
of
numerous
chemists.
The
rapid
convenient
generation
sp3-rich
complex
three-dimensional
from
simple
easily
available
aromatics
has
made
dearomatization
a
highly
valuable
synthetic
tool
for
construction
rigid
challenging
bridged
rings.
This
review
summarizes
the-state-of-the-art
advances
strategies
application
ring
formation,
discusses
their
advantages
limitations
in-depth
mechanism,
highlights
value
total
synthesis
products.
We
wish
this
will
provide
an
important
reference
medicinal
chemists
inspire
further
development
intriguing
research
area.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(47)
Published: Oct. 16, 2023
Abstract
Catalytic
asymmetric
transformations
by
dearomatization
have
developed
into
a
widely
applicable
synthetic
strategy,
but
heavily
relied
on
the
use
of
arenes
bearing
heteroatom.
In
this
case,
is
facilitated
involvement
p
‐orbital
electron
Different
from
conventional
substrate‐dependent
model,
here
we
demonstrate
that
activation
d
transition‐metal
center
can
serve
as
driving
force
for
dearomatization,
and
applied
to
development
novel
alkynyl
copper
remote
substitution
reaction.
A
newly
modified
PyBox
chiral
ligand
enables
construction
valuable
diarylmethyl
triarylmethyl
skeletons
in
high
enantioselectivities.
An
unexpected
tandem
process
involving
sequential
substitution/cyclization/1,5‐H
shift
leads
formation
enantioenriched
C−N
axis.
gram‐scale
reaction
various
downstream
highlight
robustness
method
potential
products.
Preliminary
mechanistic
studies
reveal
mononuclear
Cu‐catalyzed
process.
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:
2025,
Volume and Issue:
unknown
Published: Jan. 29, 2025
Due
to
their
strong
aromaticity
and
difficulties
in
chemo-,
regio-,
enantioselectivity
control,
asymmetric
hydrogenation
of
naphthol
derivatives
1,2,3,4-tetrahydronaphthols
has
remained
a
long-standing
challenge.
Herein,
we
report
the
first
example
homogeneous
catalyzed
by
tethered
rhodium-diamine
catalysts,
affording
wide
array
optically
pure
high
yields
with
excellent
enantioselectivities
(up
98%
yield
>99%
ee).
Mechanistic
studies
experimental
computational
approaches
reveal
that
fluorinated
solvent
1,1,1,3,3,3-hexafluoroisopropanol
(HFIP)
plays
vital
roles
control
reactivity
selectivity,
1-naphthol
is
reduced
via
cascade
reaction
pathway,
including
dearomative
tautomerization,
1,4-hydride
addition,
1,2-hydride
addition
sequence.
A
novel
synergistic
activation
mode
was
proposed
which
HFIP
assists
both
hydrogen
molecule
presence
base,
situ-generated
fleeting
keto
tautomer
immediately
trapped
Rh(III)-H
species
before
it
escapes
from
cage.
This
protocol
provides
straightforward
practical
pathway
for
synthesis
key
intermediates
several
chiral
drugs.
Particularly,
Nadolol,
drug
treatment
hypertension,
angina
pectoris,
congestive
heart
failure,
certain
arrhythmias,
enantioselectively
synthesized
time.
Chemistry - An Asian Journal,
Journal Year:
2021,
Volume and Issue:
17(4)
Published: Nov. 24, 2021
A
remarkable
growth
in
hypervalent
iodine-mediated
oxidative
transformations
as
stoichiometric
reagents
well
catalysts
has
been
well-documented
due
to
their
excellent
properties,
such
mildness,
easy
handling,
high
selectivity,
environmentally
friendly
nature,
and
stability.
This
review
aims
at
highlighting
the
asymmetric
dearomatization
reactions
involving
iodine
compounds.
The
present
article
summarizes
intra-
intermolecular
using
chiral
reagents/catalysts
followed
by
desymmetrization.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(17), P. 6606 - 6611
Published: Aug. 13, 2021
The
highly
regio-,
diastereo-,
and
enantioselective
dearomatization
reaction
of
1-substituted
2-naphthols
β,γ-alkynyl-α-imino
esters
with
complete
atom
economy
is
disclosed
via
chiral
phosphoric
acid
catalysis.
This
protocol
provides
facile
efficient
access
to
asymmetric
construction
a
broad
range
axially
allene-derived
naphthalenones
bearing
quaternary
stereocenters
in
good
yields
high
diastereoselectivities
enantioselectivities.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(13), P. 5750 - 5755
Published: March 15, 2022
Daphenylline
is
a
structurally
unique
member
of
the
triterpenoid
Daphniphyllum
natural
alkaloids,
which
exhibit
intriguing
biological
activities.
Six
total
syntheses
have
been
reported,
five
utilize
aromatization
approaches.
Herein,
we
report
concise
protecting-group-free
synthesis
by
means
novel
intramolecular
oxidative
dearomatization
reaction,
concurrently
generates
critical
seven-membered
ring
and
quaternary-containing
vicinal
stereocenters.
Other
notable
transformations
include
tandem
reductive
amination/amidation
double
cyclization
to
assemble
cage-like
architecture,
installation
other
two
chiral
stereocenters
via
highly
enantioselective
rhodium-catalyzed
challenging
hydrogenation
diene
intermediate
(90%
e.e.)
an
unprecedented
remote
acid-directed
Mukaiyama–Michael
reaction
complex
benzofused
cyclohexanone
(13:1
d.r.).
