Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Dec. 30, 2024
The
functionalized
polycycle
with
densely
contiguous
tertiary
stereocenters
is
a
formidable
challenge
in
synthesizing
the
parvistemoline
family
of
Stemona
alkaloids.
We
herein
report
their
catalytic,
asymmetric
total
syntheses
13-14
steps
from
commercially
available
2-(methoxycarbonyl)-pyrrole,
featuring
development
and
deployment
an
Ir/Pd-synergistically-catalyzed
allylation
α-non-substituted
keto
esters
secondary
aryl-substituted
alcohols,
stereodivergently
accessible
to
four
stereoisomers.
Using
chiral
Pd-enolate
Ir
π-allyl
complex
under
neutral
conditions,
no
epimerization
occurs.
Additionally,
other
two
adjacent
stereogenic
centers
can
be
installed
diastereoselectively
by
Zn(BH
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(22), P. 11165 - 11206
Published: Jan. 1, 2024
This
review
explores
the
fascinating
world
of
molecules
featuring
multiple
stereogenic
elements,
unraveling
different
strategies
designed
over
years
for
their
enantioselective
synthesis.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(35)
Published: May 16, 2024
Abstract
The
construction
of
chiral
motifs
containing
nonadjacent
stereocenters
in
an
enantio‐
and
diastereoselective
manner
has
long
been
a
challenging
task
synthetic
chemistry,
especially
with
respect
to
their
stereodivergent
synthesis.
Herein,
we
describe
protocol
that
enables
the
1,5/1,7‐nonadjacent
tetrasubstituted
through
Pd/Cu‐cocatalyzed
Heck
cascade
reaction.
Notably,
C=C
bond
relay
strategy
involving
shift
π‐allyl
palladium
intermediate
was
successfully
applied
asymmetric
1,7‐nonadjacent
stereocenters.
current
method
allows
for
efficient
preparation
molecules
bearing
two
privileged
scaffolds,
oxindoles
non‐natural
α‐amino
acids,
good
functional
group
tolerance.
full
complement
four
stereoisomers
products
could
be
readily
accessed
by
simple
combination
metal
catalysts
different
enantiomers.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(27), P. 5758 - 5763
Published: July 1, 2024
Anthrones
are
key
structural
motifs
in
many
natural
products
and
pharmaceutical
chemicals.
However,
due
to
its
unique
tricyclic
aromatic
structure,
the
synthetic
space
for
development
of
chiral
anthrone
derivatives
is
largely
limited.
By
utilizing
potential
copper-catalyzed
remote
asymmetric
yne-allylic
substitution
reaction,
we
describe
first
example
highly
regio-
enantioselective
on
various
esters
with
anthrones
under
a
mild
reaction
condition,
which
afforded
range
enantioenriched
1,3-enynes
exhibiting
broad
functional
group
tolerance
across
51
examples.
Chinese Journal of Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 24, 2025
Comprehensive
Summary
Nitrogen‐containing
bridged‐heterocycles
and
indoles
are
key
subunits
of
many
natural
products
pharmacologically
active
molecules.
We
herein
present
a
bimetallic
Cu/Ir
catalyzed
asymmetric
allylation
ketimine
esters
(
E
)‐4‐indolyl
allyl
carbonates
followed
by
acid‐promoted
Pictet‐Spengler
cyclization
sequences,
enabling
stereodivergent
synthesis
chiral
indole
fused
9‐azabicyclo[4.2.1]nonanes
containing
an
eight‐membered
ring
with
one
tertiary
two
quaternary
stereogenic
centers.
This
one‐pot
sequential
protocol
features
step
economy,
good
substrate
tolerance,
excellent
stereoselective
control.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 13, 2024
Abstract
A
synergistic
Pd/Cu
catalyst
system
has
been
developed
for
stereodivergent
transformation
of
Morita‐Baylis‐Hillman
(MBH)
carbonates
and
Schiff
bases
derived
from
simple
amino
acids
to
afford
a
series
optically
active
β‐branched
γ‐methyleneglutamic
acid
derivatives
with
adjacent
tertiary/tertiary
quaternary/tertiary
stereocenters
in
high
yields
(up
96
%)
excellent
diastereo‐
enantioselectivities
(>20/1
dr
>99
%
ee
most
cases)
under
mild
conditions.
The
use
SKP
ligand
is
disclosed
be
crucial
the
success
transformation,
particular
allowing
reaction
proceed
at
low
loading
(0.02
mol
Pd
0.08
Cu).
efficiency
catalysis
was
attributed
formation
intimate
ion
pair
complex
A1
,
composed
Pd‐phosphonium
cation
t
‐butoxide
anion,
which
would
facilitate
subsequent
deprotonation
C−C
coupling
events.
All
four
stereoisomers
glutamic
were
readily
prepared
by
permutation
enantiomers.
Synthetic
utility
methodology
exemplified
efficient
synthesis
fused
pyrrolooxazolidinone
three
contiguous
chiral
centers,
highlighting
power
asymmetric
allylic
alkylation
MBH
carbonates.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 25, 2024
The
development
of
efficient
methodologies
for
the
controlled
manufacture
specific
stereoisomers
bearing
quaternary
stereocenters
has
prompted
advances
in
a
variety
scientific
disciplines
including
pharmaceutical
chemistry,
materials
science,
and
chemical
biology.
However,
complete
control
absolute
relative
stereochemical
configurations
alkyne
derivatives
remains
an
unmet
synthetic
challenge.
Herein,
Ni/Cu
dual-catalyzed
asymmetric
propargylic
substitution
reaction
is
presented
to
produce
propargylated
products
with
all-carbon
high
yields
significant
diastereo-
enantioselectivities
(up
>20:1
dr,
>99%
ee).
synthesis
all
variants
methohexital,
widely
used
sedative-hypnotic
drug,
exemplifies
efficacy
stereodivergent
propargylation.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(43), P. 29928 - 29942
Published: Oct. 17, 2024
Chiral
tetrahydro-β-carbolines,
as
one
of
the
most
intriguing
subtypes
indole
alkaloids,
have
emerged
privileged
units
in
plenty
natural
products
and
biologically
active
molecules
with
an
impressive
range
bioactive
properties.
However,
stereodivergent
construction
these
valuable
skeletons
containing
multistereogenic
centers
from
readily
available
starting
materials
remains
very
challenging,
especially,
view
introduction
axial
chirality.
Herein,
we
developed
efficient
method
toward
enantioenriched
tetrahydro-β-carbolines
tryptophan-derived
aldimine
esters
allylic
carbonates
under
mild
reaction
conditions.
The
proceeds
a
sequential
fashion
involving
synergistic
Cu/Ir-catalyzed
allylation
Brønsted
acid-promoted
stereospecific
Pictet–Spengler
reaction,
affording
wide
chiral
bearing
up
to
four
stereogenic
good
yields
excellent
stereoselectivity
control.
When
N-aryl-substituted
were
utilized,
notably,
unique
C–N
heterobiaryl
axis
could
be
simultaneously
constructed
formation
third
point
center
last
cyclization
step
through
dynamic
kinetic
resolution
(DKR).
Computational
mechanistic
studies
established
plausible
mechanism
for
dual
asymmetric
succeeding
protonation-assisted
complete
annulation.
Structure–activity
relationship
analyses
unveil
origins
stereochemistry
building
three
centers.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 11, 2024
Chiral
2-azetines
and
allenes
are
highly
valuable
structural
units
in
natural
products
useful
chemicals.
However,
enantioselective
synthesis
of
both
has
been
extremely
challenging.
Herein,
we
present
asymmetric
construction
chiral
(70-98
%
yields
up
to
96
ee)
through
phosphine-catalyzed
[2+2]
annulation
yne-enones
with
sulfamate-derived
cyclic
imines.
These
were
easily
transformed
into
upon
treatment
Et
