Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 24, 2024
Herein,
we
report
a
method
for
enantioselective
vinylogous
addition
of
enones
to
alkoxyallenes
enabled
by
synergistic
borane/palladium
catalysis.
The
inductive
effect
provided
borane
coordination
the
ketone
was
essential
closing
gap
between
conditions
needed
generation
dienolate
and
those
initiation
palladium
catalytic
cycle
protonation
metal
catalyst.
Furthermore,
accomplished
first
example
stereodivergent
synthesis
with
chiral
borane/transition-metal
catalysts.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 27, 2025
The
absolute
and
relative
configurations
of
bioactive
chiral
molecules
are
typically
relevant
to
their
biological
properties.
It
is
thus
highly
important
desirable
construct
all
possible
stereoisomers
a
lead
candidate
or
given
natural
compound.
Synergistic
dual
catalysis
has
been
recognized
as
reliable
synthetic
strategy
for
variety
predictable
stereodivergent
transformations.
Despite
the
impressive
progress
made
in
this
field,
carbon-carbon
bond-formation
reactions
involving
stabilized
nucleophiles
remain
elusive.
Herein,
we
report
an
iridium-
magnesium-catalyzed
one-pot
sequential
allylic
alkylation/nucleophilic
alkylation
cascade
process
synthesis
four
3,3'-disubstituted
oxindoles
through
three-component
reaction.
A
diverse
array
products
readily
prepared
with
high
functional
group
compatibility
good
yields
excellent
diastereo-
enantioselectivities.
Subsequently,
total
spirooxindole
alkaloid
trigolutes
B
D
accomplished
concise
unified
route
using
same
set
starting
materials.
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.
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.
Dual
catalysis
is
a
powerful
strategy
for
developing
new
organic
reactions
that
used
to
be
challenging
achieve
by
traditional
methods.
Whether
through
relay
or
synergistic
catalysis,
it
does
not
only
facilitate
complicated
multiple
bond
formations
but
also
enriches
the
toolbox
constructing
novel
molecules.
In
this
Thieme
Cheminar,
chaired
SYNTHESIS
Editor
Jung
Min
Joo,
our
speakers
will
present
their
latest
research
on
dual
catalysis.
Speaker
line-up:
•
Weiwei
Zi
(Nankai
University)
-
“Synergistic
Catalysis
Enabled
Stereodivergent
Csp3–Csp3
Coupling
Reactions”
Philip
Wai
Hong
Chan
(Monash
“Recent
adventures
at
intersection
of
Brønsted
acid,
gold
and
photoredox
catalysis”
Chun-Jiang
Wang
(Wuhan
with
Azomethine
Ylides”
This
Cheminar
particular
interest
chemistry
students,
graduates,
researchers
in
industry
academia.
Sign
up
now
save
your
spot!
Synergistic
Reactions
Vicinal
stereocenters
are
commonly
found
natural
products,
bioactive
molecules,
potential
drugs.
Constructing
vicinal
Csp3-Csp3
formation
significant
focus
asymmetric
Over
past
five
years,
group
has
concentrated
platform
stereodivergent
coupling
using
Pd-involved
We
have
integrated
nucleophile-activation
modes
into
Pd
allowing
us
pursue
series
dienes
(including
1,3-dienes,
alkoxyallenes,
allenamides)
various
carbon
nucleophiles,
such
as
aldimine
esters,
aldehydes,
oxindoles,
pentafluorophenyl
esters.
These
provide
quick
access
variety
chiral
scaffolds
containing
manner.
Recent
One
most
synthetic
tools
emerge
over
years
rapidly
molecular
complexity
from
readily
accessible
precursors
an
enantioselective
manner
catalysis.[1]
presentation,
we
disclose
recent
contributions
field
chemical
synthesis
acid
core
these
studies.[2–5]
highlight
study
realised
method
chemo-
assembly
1,8-dihydroindeno[2,1-b]pyrroles
pyrrol-2-yl
methanols
exploited
gold(I)-
“hidden”
acid-catalysed
*β*-amino-1,4-enynols.[2–4]
presence
*N*-triflyl
phosphoramide,
tandem
dehydrative
Nazarov-type
electrocyclisation/hydroamination
substrate
was
selectively
occur
afford
synthetically
useful
indeno-fused
pyrrole
derivative.[6]
On
other
hand,
changing
phosphoric
observed
result
hydroamination/enantioselective
formal
1,3-allylic
alcohol
isomerisation
cascade
give
1*H*-pyrrole.
An
electron-donor
acceptor
complex,
generated
Hantzsch
ester
*N*-(acyloxy)phthalimide
ester,
catalytic
system
enable
Minisci-type
C2-alkylation
quinolines,
isoquinolines
pyridines
under
blue
light
emitting
diode
(456
nm)
discussed.[5]
Ylides
emerged
reaction
development
Through
effect
between
different
systems,
simultaneous
activation
components
can
realized,
which
effectively
reduces
barriers
improves
activity
efficiency,
thus
realizing
transformations
impossible
inefficient
mono-catalysis,
especially
molecules
stereogenic
centers.
I
report
progress
metallated
azomethine
ylides
stereochemically
controllable
nucleophilic
reagents.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 27, 2024
Vinylaziridines
are
important
building
blocks
in
organic
chemistry,
especially
the
synthesis
of
nitrogen-containing
heterocycles.
The
direct
and
efficient
transfer
an
appropriate
nitrogen
source
to
readily
accessible
conjugated
dienes
is
a
notable
methodology.
Pd-catalyzed
oxidative
1,2-difunctionalization
through
π-allyl-palladium
species
should
be
ideal
method
for
selective
vinylaziridines.
However,
this
faces
challenge
regioselectivity,
often
resulting
1,4-difunctionalization
instead.
In
study,
we
developed
aerobic
via
achieve
regio-,
site-
stereo-selective
aziridination
under
synergistic
effects
Pd
