Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(21)
Published: March 21, 2024
Abstract
The
construction
of
two
distal
stereocenters
through
a
single
catalytic
process
is
great
interest
in
organic
synthesis.
While
there
are
some
successful
reports
regarding
stereodivergent
preparation
1,3‐
or
1,4‐stereocenters,
the
more
challenged
1,5‐nonadjacent
have
never
been
achieved
fashion.
Herein
we
describe
synergistic
palladium/copper
catalysis
for
1,4‐difunctionalization
reactions
1,3‐dienes,
providing
access
to
quaternary
stereocenters.
Because
each
catalysts
separately
controlled
one
newly
formed
stereocenters,
synthesis
all
four
diastereomers
products
could
readily
be
simply
by
choosing
an
appropriate
combination
chiral
catalysts.
Experimental
and
computational
studies
supported
mechanism
involving
Heck/Tsuji–Trost
cascade
reaction,
origins
stereoselectivity
were
elucidated.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(6), P. 3812 - 3844
Published: Feb. 23, 2024
Chiral
skeletons
with
multiple
stereogenic
centers
widely
reside
in
nature
and
drugs,
their
relative
absolute
configuration
often
determine
physiological
or
pharmacological
properties.
Stereodivergent
synthesis
of
chiral
molecules
is
not
only
great
significance,
but
also
highly
challenging
since
the
formation
one
diastereomers
inherently
preferred
most
asymmetric
reactions.
dual
catalysis,
introduced
2013
by
Carreira
group,
perfectly
catered
to
all
requirements
for
full
stereoselectivity
control
given
reactions
two
catalysts
are
utilized
a
synergistic
way
act
independently,
has
now
been
arguably
efficient
strategy
realize
stereodivergent
synthesis.
This
comprehensive
review
presents
an
overview
development
enabled
catalysis
past
ten
years,
providing
readers
fundamental
attributes
as
well
ability,
scope,
mechanism,
limitations
this
strategy.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(25)
Published: April 16, 2024
Aminocatalysis
is
a
well-established
tool
that
enables
the
production
of
enantioenriched
compounds
under
mild
conditions.
Its
versatility
underscored
by
its
seamless
integration
with
various
synthetic
approaches.
While
combination
aminocatalysis
metal
catalysis,
photochemistry,
and
stoichiometric
oxidants
has
been
extensively
explored,
synergy
electrochemical
activation
remains
largely
unexplored.
Herein,
we
present
successful
merger
electrochemistry
to
perform
SOMO-type
transformations,
expanding
toolkit
for
asymmetric
synthesis.
The
methodology
harnesses
electricity
drive
oxidation
catalytically
generated
enamines,
which
ultimately
partake
in
enantioselective
radical
processes,
leading
α-alkylated
aldehydes.
Crucially,
mechanistic
studies
highlight
how
this
strategy
enabled
use
redox
shuttle,
4,4'-dimethoxybiphenyl,
prevent
catalyst
degradation
furnishing
coveted
good
yield
high
enantioselectivity.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(13), P. 9404 - 9412
Published: March 20, 2024
The
catalytic
and
enantioselective
construction
of
quaternary
(all-carbon
substituents)
stereocenters
poses
a
formidable
challenge
in
organic
synthesis
due
to
the
hindrance
caused
by
steric
factors.
One
conceptually
viable
potentially
versatile
approach
is
coupling
C–C
bond
through
an
outer-sphere
mechanism,
accompanied
realization
enantiocontrol
cooperative
catalysis;
however,
examples
such
processes
are
yet
be
identified.
Herein,
we
present
method
for
creating
different
compounds
with
photoredox/Fe/chiral
primary
amine
triple
catalysis.
This
facilitates
connection
unactivated
alkyl
source
tertiary
moiety,
which
also
rare.
scalable
process
exhibits
mild
conditions,
does
not
necessitate
use
base,
possesses
good
functional-group
tolerance.
Preliminary
investigations
into
underlying
mechanisms
have
provided
valuable
insights
reaction
pathway.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(21)
Published: March 21, 2024
Abstract
The
construction
of
two
distal
stereocenters
through
a
single
catalytic
process
is
great
interest
in
organic
synthesis.
While
there
are
some
successful
reports
regarding
stereodivergent
preparation
1,3‐
or
1,4‐stereocenters,
the
more
challenged
1,5‐nonadjacent
have
never
been
achieved
fashion.
Herein
we
describe
synergistic
palladium/copper
catalysis
for
1,4‐difunctionalization
reactions
1,3‐dienes,
providing
access
to
quaternary
stereocenters.
Because
each
catalysts
separately
controlled
one
newly
formed
stereocenters,
synthesis
all
four
diastereomers
products
could
readily
be
simply
by
choosing
an
appropriate
combination
chiral
catalysts.
Experimental
and
computational
studies
supported
mechanism
involving
Heck/Tsuji–Trost
cascade
reaction,
origins
stereoselectivity
were
elucidated.
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.
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.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(11), P. 8160 - 8167
Published: May 10, 2024
Rhodium(III)-catalyzed
enantioselective
C–H
activation
has
emerged
as
a
powerful
tool
for
assembling
enabling
chiral
molecules.
However,
this
approach
is
significantly
hampered
by
the
cumbersome
synthetic
routes
preparing
rhodium
catalysts.
In
sharp
contrast,
we
herein
report
on
an
electrochemical
domino
catalysis
system
that
exploits
achiral
Cp*-rhodium
catalyst
along
with
easily
accessible
Brønsted
base
activation/annulation
reaction
of
alkenes
benzoic
acids.
Our
strategy
offers
environmentally
benign
and
most
user-friendly
synthetically
useful
phthalides
in
good
enantioselectivity,
employing
electricity
sustainable
oxidant.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(26), P. 10135 - 10145
Published: Jan. 1, 2024
A
stereodivergent
synthesis
of
chiral
ζ-hydroxy
amino
esters
containing
1,6-stereocenters
and
a
unique
β,γ-unsaturation
was
developed
through
asymmetric
Cu/Ru
relay
catalysis
to
conduct
the
borrowing
hydrogenation/1,6-Michael
addition
protocol.
