Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Oct. 9, 2023
Abstract
Transition
metal-catalyzed
asymmetric
hydrofunctionalizations
of
unsaturated
bonds
via
π-ƞ
3
substitution
have
emerged
as
a
reliable
method
to
construct
stereogenic
centers,
and
mainly
rely
on
the
use
heteroatom-based
or
carbon
nucleophiles
bearing
acidic
C-H
bonds.
In
comparison,
sp
2
are
generally
not
under
consideration
because
enormous
challenges
in
cleaving
corresponding
inert
Here,
we
report
protocol
achieve
formal
hydrocarbonations,
including
hydroalkenylation,
hydroallenylation
hydroketenimination
both
1,3-dienes
alkynes
hydroalkylation
Wittig
reaction
cascade.
A
series
unachievable
motifs
hydrofunctionalizations,
such
di-,
tri-
tetra-substituted
alkenes,
allenes,
tri-substituted
ketenimines
allyl
skeletons
all
facilely
constructed
high
regio-,
diastereo-
enantioselectivities
with
this
cascade
design.
Stereodivergent
synthesis
four
stereoisomers
1,4-diene
stereocenter
Z/E-controllable
olefin
unit
highlights
power
present
protocol.
An
interesting
mechanistic
feature
is
revealed
that
alkyne
actually
undergoes
hydrocarbonation
formation
conjugated
diene
intermediate,
different
from
conventional
viewpoint
hydrofunctionalization
only
involves
allene
species.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(7), P. 4199 - 4207
Published: Feb. 13, 2023
Spirooxindoles
have
emerged
as
promising
architectures
for
engineering
biologically
active
compounds.
The
diastereodivergent
construction
of
unique
scaffolds
this
type
with
full
control
continuous
chiral
centers
including
an
all-carbon
quaternary
stereogenic
center
is
yet
to
be
developed.
Here,
we
report
unprecedented
desymmetric
[3
+
3]
annulation
oxabicyclic
alkenes
enals
enabled
by
N-heterocyclic
carbene
(NHC)/Rh
cooperative
catalysis,
leading
a
series
enantiomerically
enriched
spirooxindole
lactones
excellent
enantioselectivities
(up
>99%
ee)
and
diastereoselectivities
>95:5
dr).
combined
catalyst
system
comprises
rhodium
complex
that
controls
the
configuration
at
electrophilic
carbon
NHC
nucleophilic
oxindole-containing
carbon;
thus,
four
stereoisomers
products
can
readily
obtained
simply
switching
configurations
two
catalysts.
Transformations
spirooxindoles
delivered
synthetically
useful
Importantly,
those
arrested
mammalian
cells
in
mitosis
exhibited
potent
antiproliferative
activities
against
HeLa
cells.
Significantly,
both
absolute
relative
exert
prominent
effects
on
bioactivities,
underscoring
great
importance
catalytic
asymmetric
synthesis
beyond
creating
tools
exploration
structure–activity
relationships.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(14), P. 8657 - 8739
Published: July 2, 2024
Chiral
phosphorus
ligands
play
a
crucial
role
in
asymmetric
catalysis
for
the
efficient
synthesis
of
useful
optically
active
compounds.
They
are
largely
categorized
into
two
classes:
backbone
chirality
and
P-stereogenic
ligands.
Most
reported
belong
to
former
class.
Privileged
ones
such
as
BINAP
DuPhos
frequently
employed
wide
range
catalytic
transformations.
In
contrast,
latter
class
has
remained
small
family
many
years
mainly
because
their
synthetic
difficulty.
The
late
1990s
saw
emergence
novel
with
superior
enantioinduction
ability
Rh-catalyzed
hydrogenation
reactions.
Since
then,
numerous
have
been
synthesized
used
This
Review
summarizes
thus
far,
including
stereochemical
electronic
properties
that
afford
high
excellent
enantioselectivities.
Examples
reactions
use
this
described
together
applications
construction
key
intermediates
natural
products
therapeutic
agents.
literature
covered
dates
back
1968
up
until
December
2023,
centering
on
studies
published
later
years.
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:
2022,
Volume and Issue:
62(2)
Published: Nov. 16, 2022
Abstract
Synergistic
catalysis
has
emerged
as
one
of
the
most
powerful
tools
for
stereodivergent
formation
Csp
3
−Csp
bonds
bearing
vicinal
stereocenters.
Despite
many
successes
that
have
been
achieved
in
this
field,
coupling
reactions
involving
stabilized
nucleophiles
remain
challenging
because
competing
single‐catalysis
pathway.
Herein,
we
report
a
synergistic
palladium/phase‐transfer
catalyst
system
enables
diastereodivergent
1,3‐dienes
with
nucleophile
oxindoles.
Both
syn
and
anti
products,
quaternary
tertiary
stereocenters,
could
be
selectively
produced
good
yields
high
enantio‐
diastereoselectivities.
Non‐covalent
activation
via
chiral
ion
pair
biphasic
is
crucial
success
factor
achieving
diastereodivergence.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: May 22, 2023
We
herein
describe
an
asymmetric
α-allylic
allenylation
of
β-ketocarbonyls
and
aldehydes
with
1,3-enynes.
A
synergistic
chiral
primary
amine/Pd
catalyst
was
identified
to
facilitate
the
utilization
1,3-enynes
as
atom-economic
achiral
allene
precursors.
The
catalysis
enables
construction
all-carbon
quaternary
centers-tethered
allenes
bearing
non-adjacent
1,3-axial
central
stereogenic
centers
in
high
level
diastereo-
enantio-selectivity.
By
switching
configurations
ligands
aminocatalysts,
diastereodivergence
can
be
achieved
any
four
diastereoisomers
accessed
enantio-
selectivity.
Precision Chemistry,
Journal Year:
2024,
Volume and Issue:
2(5), P. 208 - 220
Published: April 23, 2024
The
catalytic
asymmetric
diastereodivergent
synthesis
of
axially
chiral
2-alkenylindoles
was
established
via
phosphoric
acid-catalyzed
addition
reactions
C3-unsubstituted
with
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(10), P. 6422 - 6437
Published: March 1, 2024
The
development
of
a
new
catalytic
strategy
plays
vital
role
in
modern
organic
chemistry
since
it
permits
bond
formation
an
unprecedented
and
more
efficient
manner.
Although
the
application
preformed
metal
complexes
as
π-base-activated
reagents
have
enabled
diverse
transformations
elegantly,
concept
by
directly
utilizing
transition
metals
π-Lewis
base
catalysts
remain
underdeveloped,
especially
field
asymmetric
catalysis.
Here,
we
outline
our
perspective
on
discovery
palladium(0)
catalyst,
which
is
capable
increasing
highest
occupied
molecular
orbital
(HOMO)
energy
both
electron-neutral
electron-deficient
1,3-dienes
1,3-enynes
upon
flexible
η2-complexes
formed
situ
resultant
π-backdonation.
Thus,
fruitful
carbon–carbon-forming
reactions
with
electrophiles
can
be
achieved
enantioselectively
vinylogous
addition
pattern,
conceptually
different
from
classical
oxidative
cyclization
mechanism.
Emphasis
will
given
to
mechanism
elucidation,
features,
reaction
design
together
further
this
emerging
field.
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.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 31, 2024
ConspectusTransition-metal-catalyzed
coupling
reactions
of
dienes
(such
as
1,3-dienes,
alkoxyallenes,
and
aminoallenes)
with
carbon
nucleophiles
have
proven
to
be
a
highly
effective
method
for
creating
Csp3–Csp3
bonds.
These
perfect
atom
economy
typically
occur
under
mild
reaction
conditions.
By
using
chiral
metal
complexes
catalysts,
it
is
possible
create
enantioenriched
molecules
bearing
allylic
stereocenters
high
enantioselectivities.
However,
challenges
arise
when
bonds
two
vicinal
are
constructed
through
this
type
reaction.
Due
the
inherent
diastereoselectivities,
only
kinetically
favored
diastereoisomers
(either
syn-
or
anti-product)
usually
obtained
transition-metal
catalyst
system.
Achieving
complementary
stereoisomers
selectivity,
which
require
complete
control
both
absolute
relative
configurations
multiple
centers
in
single
chemical
transformation,
impossible.Over
past
decade,
significant
advancements
been
made
stereodivergent
synthesis.
Notably,
iridium-related
synergistic
catalysis
has
rapidly
developed
alkylation
reactions.
these
systems
were
limited
alcohol
derivatives
electrophilic
partners.
Finding
ways
extend
use
other
types
crucial
issue
that
needs
addressed.In
2019,
we
reported
first
palladium-mediated
system
between
1,3-dienes
aldimine
esters.
Lately,
strategy
successful
accessing
diverse
substrate
patterns.
In
Account,
will
summarize
our
laboratory's
efforts
developing
range
palladium-involved
dienes.
We
discovered
several
systems,
including
Pd/Cu(Ag),
Pd/amine,
Pd/Lewis
base,
Pd/PTC.
Additionally,
dienes,
such
aminoallenes,
serve
suitable
partners
coupling.
processes
provide
an
efficient
constructing
scaffolds
stereocenters.
Density
functional
theory
(DFT)
calculations
performed
elucidate
mechanism
rationalize
origins
stereochemistry
some
systems.
Finally,
synthetic
application
methods
demonstrated
concise
total
synthesis
number
natural
products
bioactive
molecules.
It
anticipated
increasing
chemists
join
research
on
contribute
more
elegant
examples
area.
believe
future
development
further
push
boundary
asymmetric
find
innovative
applications
soon
synthesizing
complex
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(40)
Published: June 27, 2022
Catalysis
by
excited-state
palladium
has
emerged
as
an
active
area
of
research,
but
controlling
the
enantioselectivity
remains
a
challenge.
Herein,
we
report
use
synergistic
Pd/Cu
catalysis
to
accomplish
first
three-component
photochemical
1,4-bisalkylation
reactions
1,3-butadiene.
Consequently,
α-amino
acid
esters
bearing
quaternary
stereocenters
were
expeditiously
synthesized
from
three
simple
starting
materials:
alkyl
bromide,
butadiene,
and
aldimine
ester.
Experimental
computational
investigation
reaction
mechanism
confirmed
radical
pathway
involving
species.
The
stereochemistry
is
mainly
controlled
chiral
Cu
catalyst.