Angewandte Chemie,
Год журнала:
2024,
Номер
136(35)
Опубликована: Май 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,
Год журнала:
2024,
Номер
146(13), С. 9241 - 9251
Опубликована: Март 19, 2024
Much
attention
has
been
focused
on
the
catalytic
asymmetric
creation
of
single
chiral
centers
or
two
adjacent
stereocenters.
However,
construction
nonadjacent
stereocenters
is
significant
importance
but
challenging
because
lack
remote
induction
models.
Herein,
based
a
C═C
bond
relay
strategy,
we
report
synergistic
Pd/Cu-catalyzed
1,5-double
model.
All
four
stereoisomers
target
products
bearing
1,5-nonadjacent
involving
both
allenyl
axial
and
central
chirality
could
be
obtained
divergently
by
simply
changing
combination
catalysts
with
different
configurations.
Control
experiments
DFT
calculations
reveal
novel
mechanism
1,5-oxidative
addition,
contra-thermodynamic
η3-allyl
palladium
shift,
conjugate
nucleophilic
substitution,
which
play
crucial
roles
in
control
reactivity,
regio-,
enantio-,
diastereoselectivity.
It
expected
that
this
strategy
may
provide
general
protocol
for
synthesis
structural
motifs
distant
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(21)
Опубликована: Март 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,
Год журнала:
2024,
Номер
63(35)
Опубликована: Май 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,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 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.
Organic Letters,
Год журнала:
2024,
Номер
26(27), С. 5788 - 5793
Опубликована: Июнь 27, 2024
Stereocontrolled
oxa-Michael
additions
are
challenging,
given
the
high
reversibility
of
process,
which
ultimately
leads
to
racemization
newly
formed
stereocenters.
When
iron-catalyzed
borrowing
hydrogen
from
allylic
alcohols
was
combined
with
a
stereocontrolled
organocatalytic
addition,
wide
array
chiral
tetrahydropyrans
were
efficiently
prepared.
The
reaction
could
be
performed
in
diastereoselective
manner
pre-existing
stereocenters
or
enantioselectively
achiral
substrates.
key
success
reactivity
iron
complex,
selective
for
alcohol
dehydrogenation
and
irreversibly
led
final
product.
Chemical Science,
Год журнала:
2024,
Номер
15(26), С. 10135 - 10145
Опубликована: Янв. 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.
Synthesis,
Год журнала:
2024,
Номер
56(22), С. 3349 - 3364
Опубликована: Март 5, 2024
Abstract
Transition-metal-catalyzed
asymmetric
allylic
substitution
reactions
represent
a
hot
research
topic
in
the
field
of
synthesis,
with
significant
progress
having
been
made.
Among
diverse
catalysis
systems,
relay
enables
sequential
activation
multiple
steps
one
pot
and
rapid
construction
chiral
centers,
providing
simple
powerful
platform
for
organic
synthesis.
Recently,
has
successfully
applied
to
reactions,
variety
challenging
transformations
have
realized.
This
Short
Review
summarizes
related
on
based
over
last
decade.
1
Introduction
2
The
General
Transformation
Model
3
Allylation
Relays
Further
Reaction
4
Initial
5
Conclusion
Outlook
Abstract
In
the
quest
for
more
rapid
and
eco‐compatible
preparation
of
complex
molecules
from
widely
available
ones,
borrowing
hydrogen
is
one
most
elegant
manners
to
directly
functionalize
alcohols.
Such
catalytic
cycles
reduce
synthetic
cost,
avoid
waste
additional
steps
associated
with
adjusting
redox
state
functionalization
carbon
chains.
this
field,
last
ten
years
have
seen
development
general
strategies
control
absolute
stereochemistry
created
molecules.
This
enantiocontrol
can
arise
three
distinct
cycle,
namely
initial
dehydrogenation,
carbonyl
or
final
back‐transfer.
review
presents
different
enantioselective
approaches
developed
according
these
principles
highlights
great
potential
transformations,
current
limitations
future
challenges.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(43), С. 29928 - 29942
Опубликована: Окт. 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.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 2, 2025
Current
synthetic
transformations
occur
readily
with
starting
materials
that
possess
both
innate
reactivity
and
steric
accessibility
or
functional-group-oriented
reactivity.
However,
achieving
reactions
inactive
feedstock
substrates
remains
significantly
challenging
normally
requires
cumbersome
prior
functional
group
manipulations.
Herein,
we
report
an
unprecedented
example
of
catalytic
asymmetric
1,3-dipolar
cycloaddition
azomethine
ylides
nonactivated
alkenes
enabled
by
copper/ruthenium
relay
catalysis.
Key
to
the
success
is
temporary
activation
strategy
initiated
oxidative
dehydrogenation
inert
allylic
alcohols
into
electron-demanding
reversed
highly
reactive
enones,
which
triggers
ensuing
Cu-catalyzed
followed
reductive
hydrogenation
deliver
functionalized
chiral
pyrrolidines
construction
two
C-C
bonds
four
well-defined
stereogenic
centers
in
atom-/step-economical
redox-neutral
manner.
This
method
features
mild
reaction
conditions,
operational
simplicity,
broad
substrate
scope
also
characterized
formal
dynamic
kinetic
resolution.
Mechanistic
studies
control
experiments
supported
a
typical
borrowing-hydrogen
cascade
orthogonally
merged
revealed
superiority
reliability
catalysis
are
controlled
release
but
unstable
enones
impede
undesired
polymerization.
It
should
be
noted
up
stereoisomers
otherwise
inaccessible
cyclobutanes
could
prepared
through
concise
late-stage
elaborations.
