Abstract
Organocatalytic
dearomatization
of
β‐naphthols
has
been
achieved
via
a
1,6‐conjugated
addition
2‐naphthols
to
alkynyl
7‐methylene‐7
H
‐indoles
in
situ
generated
from
α‐(7‐indolyl)methanols.
In
the
presence
racemic
phosphoric
acid,
series
tetrasubstituted
allenes
was
obtained
high
yields.
Particularly,
with
aid
chiral
asymmetric
investigated,
affording
axially
moderate
enantioselectivity.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Jan. 15, 2024
Abstract
The
construction
of
N–N
axially
chiral
motifs
is
an
important
research
topic,
owing
to
their
wide
occurrence
in
natural
products,
pharmaceuticals
and
ligands.
One
efficient
method
the
atroposelective
dihydropyrimidin-4-one
formation.
We
present
herein
a
direct
catalytic
synthesis
atropisomers
with
simultaneous
creation
contiguous
axial
central
chirality
by
oxidative
NHC
(
N
-heterocyclic
carbenes)
catalyzed
(3
+
3)
cycloaddition.
Using
our
method,
we
are
able
synthesize
structurally
diverse
pyrroles
indoles
vicinal
or
bearing
2,3-dihydropyrimidin-4-one
moiety
moderate
good
yields
excellent
enantioselectivities.
Further
synthetic
transformations
obtained
derivative
products
demonstrated.
reaction
mechanism
origin
enantioselectivity
understood
through
DFT
calculations.
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.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 28, 2025
Herein,
we
report
a
novel
squaramide
containing
chiral
bifunctional
N-heterocyclic
carbene
(NHC)
and
its
utilization
in
developing
asymmetric
intramolecular
conjugate
addition
involving
noncovalent
interaction.
Via
concomitant
activation
of
both
electrophilic
nucleophilic
centers
substrates,
the
reaction
proceeds
through
well-organized
transition
state,
thereby
affording
products
with
up
to
94%
ee
broad
scope.
The
process
is
found
be
scalable.
initial
mechanistic
study
supports
nature
newly
designed
NHC.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 5211 - 5218
Published: March 12, 2025
The
asymmetric
electrophilic
amination
using
azodicarboxylates
as
the
N-source
for
construction
of
C–N
bond
has
attracted
much
attention
over
past
decades.
However,
use
in
situ
formed
nucleophilic
intermediates,
rather
than
bench-stable
reagents,
remains
elusive
and
challenging.
Herein,
we
disclose
an
enantioselective
reaction
generated
alkylgold
species
with
under
a
gold
complex
chiral
quinine-derived
squaramide
(QN-SQA)
synergetic
catalysis,
leading
to
alkylideneoxazolines
nitrogen-containing
tertiary
carbon
stereocenter
good
high
yields
enantioselectivities.
Moreover,
starting
from
same
oxazoles
incorporating
aminomethyl
group
on
5-position
could
be
obtained
by
Brønsted
acid
relay
catalysis
via
alkylideneoxazoline
species.
This
method
offers
complementary
approach
through
interception
With
this
strategic
protocol,
further
synthetic
applications
can
envisioned
catalytic
C–C
C–X
bonds.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(36), P. 7479 - 7483
Published: Aug. 2, 2024
The
field
of
asymmetric
catalysis
has
been
developed
by
exploring
noncovalent
interactions,
particularly
within
N-heterocyclic
carbene-mediated
processes.
Despite
challenges
due
to
the
limited
number
compatible
electrophiles
(predominantly
π-acceptors),
this
study
introduces
first
α-alkylation
3-aryl
oxindoles
using
C
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(25), P. 4740 - 4744
Published: June 21, 2023
Reported
herein
is
the
catalytic
asymmetric
aminative
dearomatization
reaction
of
common
phenols.
As
opposed
to
well-studied
indoles
and
naphthols,
phenols
are
supposed
be
challenging
substrates
for
reactions
in
terms
their
strong
aromaticity
regioselectivity
issues.
Under
catalysis
a
chiral
phosphoric
acid,
C4-regiospecific
with
azodicarboxylates
readily
occurred
at
ambient
temperature,
delivering
an
array
biologically
synthetically
important
aza-quaternary
carbon
cyclohexadieneones
good
yields
excellent
enantioselectivities
(29
examples,
up
98%
yield,
>99%
ee).
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 3, 2024
An
asymmetric
addition/cyclization
cascade
of
amidoesters
and
iminoquinones
is
developed
using
noncovalent
N-heterocyclic
carbene
(NHC)
catalysis.
The
process
enables
access
to
various
functionalized
benzofuranones
with
an
all-carbon
quaternary
stereocenter
high
yields
ee
values.
reaction
displays
a
broad
substrate
scope.
Via
product
modifications,
enantioenriched
synthesis
biologically
relevant
spirocyclic
lactones
lactams
achieved.
Substrate
activation
via
interaction
NHC
suggested
for
the
process.
