Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
29(15)
Published: Dec. 19, 2022
The
expeditious
construction
of
complex
molecules
having
multiple
stereocentres
is
highly
desirable
in
organic
chemistry.
In
the
present
communication,
we
report
development
an
organocatalytic
asymmetric
desymmetrization
prochiral
enal-tethered
cyclohexadienones
via
C3-selective
Friedel-Crafts
alkylation
indoles
triggered
by
LUMO-lowering
iminium
activation/HOMO-raising
enamine
activation.
reaction
provides
access
to
bicyclic
enones,
which
further
undergo
acid-mediated
intramolecular
annulation
from
C2-position
afford
strained
cyclohepta[b]indoles
with
five
contiguous
and
three
new
C-C
bonds
excellent
enantioselectivity
diastereoselectivity.
Organic Chemistry Frontiers,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
The
highly
regio-
and
diastereoselective
substitution-hemiketalization
cyclization
of
bridged
benzoxocin-4-ones
with
Grignard
reagents
is
reported
to
enable
a
facile
synthesis
diverse
portfolio
benzoxocin-2-ol
frameworks.
Organic Chemistry Frontiers,
Journal Year:
2020,
Volume and Issue:
8(4), P. 825 - 843
Published: Dec. 21, 2020
This
review
describes
recent
developments
in
the
asymmetric
transformations
of
achiral
cyclohexadienones,
including
enantioselective
desymmetrization
prochiral
cyclohexadienones
and
kinetic
resolution
racemic
cyclohexadienones.
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:
2024,
Volume and Issue:
26(4), P. 839 - 844
Published: Jan. 22, 2024
An
efficient
method
for
the
stereoselective
synthesis
of
"all
center
substituted"
polycyclic
pyrazoles
from
alkynyl
cyclohexa-2,5-dienones
and
nonstabilized
diazoalkanes
via
sequential
[3
+
2]-cycloaddition/[1,5]-sigmatropic
rearrangement
aza-Michael
reactions
is
reported.
The
developed
process
highly
regioselective
stereoselective.
It
employs
a
wide
substrate
scope
to
furnish
structurally
diverse
linear
bridged
[4.4.n.0]
ring-fused
in
moderate
good
yields.
One-pot
gram-scale
syntheses
synthetic
transformations
have
also
been
showcased.
The Chemical Record,
Journal Year:
2021,
Volume and Issue:
21(12), P. 3689 - 3726
Published: June 19, 2021
The
development
of
transition-metal
catalyzed
enantioselective
and
diastereoselective
transformations
has
contributed
many
advances
in
the
field
synthetic
organic
chemistry.
Particularly,
stereoselective
desymmetrization
prochiral
cyclohexadienones
represents
a
powerful
strategy
for
accessing
highly
functionalized
stereochemically
enriched
scaffolds,
which
are
often
found
biologically
active
compounds
natural
products.
In
recent
years,
several
research
groups
including
our
group
have
made
significant
progress
on
desymmetrizations
2,5-cyclohexadienones.
this
account,
we
will
provide
an
overview
developments
area
employing
Pd,
Cu,
Rh,
Au,
Ag,
Ni,
Co,
Mn-catalysts.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(26), P. 3795 - 3811
Published: Jan. 1, 2023
Prochiral
2,5-cyclohexadienones,
being
stable
and
easily
accessible,
are
privileged
key
building
blocks
for
the
synthesis
of
complex
molecules
bioactive
natural
products.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(9), P. 5977 - 5986
Published: Feb. 23, 2024
While
the
Pd(0)-catalyzed
cyclization
of
alkyne-tethered
unsaturated
carbonyl
substrates
has
been
reported,
mechanism
not
well
elucidated,
and
potential
asymmetric
version
remains
to
be
developed.
Here,
we
disclose
that
a
chiral
Pd(0)
complex
can
efficiently
promote
desymmetrizative
cyclohexadienones
in
CH3OH,
resultant
Pd(II)
intermediates
further
undergo
an
array
tandem
coupling
reactions,
including
Suzuki,
Sonogashira,
even
chemoselective
reduction
by
CH3OH
absence
additional
partners.
As
result,
broad
spectrum
hydrobenzofuran
derivatives,
having
tetra-
or
trisubstituted
exo-alkene
motif,
is
constructed
with
moderate
outstanding
enantioselectivity
exclusive
cis-difunctionalization
pattern.
In
addition,
this
enantioselective
protocol
expanded
linear
carbonyls,
new
cyclization/coupling
cascade
bis-alkyne-tethered
enones
realized
efficiently,
furnishing
diversely
structured
frameworks
high
stereoselectivity.
Moreover,
kinetic
transformation
for
various
racemic
accomplished
under
similar
catalytic
conditions,
unusual
reactions
chemoselectively
undertaking
Suzuki
Sonogashira
coupling,
occur
sequentially,
finally
yielding
two
types
products,
both
via
either
ligand-
substrate-based
control.
The
experimental
results
demonstrate
current
Pd(0)-based
strategy
superior
classical
Pd(II)-catalyzed
carbopalladation/cyclization
process
identical
regard
synthetic
versatility.
density
functional
theory
calculations
are
conducted
rationalize
oxidative
cyclometalation
pathway
key
step,
which
leads
observed
cis-difunctionalized
products
exclusively.
