Chemical Society Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 11, 2024
Catalytic
asymmetric
conjugate
additions
of
carbon
nucleophiles
have
emerged
as
a
potent
tool
for
constructing
multi-stereogenic
molecules
with
precise
stereochemical
control.
This
review
explores
the
concept
diastereodivergence
in
such
reactions,
focusing
on
strategies
to
achieve
selective
access
diverse
diastereomeric
products
upon
carbon-carbon
bond
formation.
Drawing
from
rich
array
examples,
we
delve
into
key
approaches
controlling
outcome
these
transformations,
including
alteration
alkene
geometry,
fine-tuning
reaction
parameters,
synergistic
catalysis,
and
isomerization
adducts.
Additionally,
highlight
iterative
additions,
showcasing
their
potential
diastereodivergent
synthesis
methyl-branched
stereocenters
1,3-relationships.
By
presenting
concentrated
overview
this
significant
topic,
aims
provide
valuable
insights
design
execution
stereodivergent
catalytic
offering
new
avenues
advancing
stereoselective
structural
diversity
organic
synthesis.
Chemical Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 3, 2024
Stereodivergent
synthesis
of
chiral
δ-valerolactones
bearing
a
unique
azaarene-containing
α-quaternary
and
tertiary
stereocenter
was
enabled
by
Cu/Ru
relay
catalysis
via
cascade
borrowing
hydrogen/Michael
addition/lactonization
protocol.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 10, 2024
A
Pd/C-catalyzed
dehydrogenative
[3
+
2]
cycloaddition
is
described
for
the
diastereoswitchable
synthesis
of
hexahydropyrrolo[2,1-a]isoquinolines
by
altering
solvents.
The
reaction
proceeds
through
a
sequential
formation
azomethine
ylides
from
tetrahydroisoquinoline
acetates
and
1,3-dipolar
with
2-nitroethenylbenzenes.
This
method
displayed
tunable
diastereoselectivity,
broad
substrate
scope
good
functional
group
compatibility.
Moreover,
gram-scale
selective
reductive
or
oxidative
transformations
product
further
demonstrate
utility
this
methodology.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(45)
Опубликована: Июль 11, 2024
Here,
we
report
a
strategy
enabling
triple
switchable
chemo-,
regio-,
and
stereodivergence
in
newly
developed
palladium-catalyzed
cycloadditions
of
allenes.
An
asymmetric
pseudo-stereodivergent
cycloaddition
allenes
bearing
primary
leaving
group
at
the
α-position,
where
dynamic
kinetic
hydroalkoxylation
racemic
unactivated
was
enantio-determining
step,
is
realized,
providing
four
stereoisomers
[(Z,R),
(Z,S),
(E,S),
(E,R)]
containing
di-substituted
alkene
scaffold
stereogenic
center.
By
tuning
reaction
conditions,
mechanistically
distinctive
uncovered
selectively
with
same
set
substrates.
switching
position
allenes,
involving
an
intermolecular
O-attack
disclosed.
Diverse
mechanisms
reactions
enable
rapid
access
to
structurally
stereochemically
diverse
3,4-dihydro-2H-1,4-benzoxazines
high
efficiency
selectivity.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(11), С. 3033 - 3040
Опубликована: Янв. 1, 2024
Chiral
spiropyrazolones
were
constructed
through
Pd-catalyzed
asymmetric
sequential
hydroalkylation
of
1,3-enynes.
Four
stereoisomers
could
be
obtained
substrate
control
and
chiral
ligand
control.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(32)
Опубликована: Май 23, 2024
Abstract
Sterically
hindered
pyridines
embedded
in
a
three‐dimensional
triptycene
framework
have
been
synthesized,
and
their
resolution
by
chiral
HPLC
enabled
access
to
unprecedented
enantiopure
exceeding
the
known
steric
limits.
The
design
principles
for
new
axially
pyridine
derivatives
are
then
described.
To
rationalize
associations
with
Lewis
acids
transition
metals,
comprehensive
determination
of
electronic
parameters
this
class
was
performed.
This
led
general
parameterization
(percent
buried
volume
%V
Bur
,
Tolman
cone
angle
θ,
He
8
_steric
descriptor)
large
set
two‐
derivatives.
These
shown
describe
quantitatively
interactions
carbon‐
boron‐centered
were
used
predict
ΔG°
association
prototypical
B(C
6
F
5
)
3
acid
widely
frustrated
pair
catalysis.
first
sterics
is
fundamental
basis
future
development
predictive
reactivity
models
guiding
applications
bulky
organocatalysis,
pairs,
transition‐metal
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(32)
Опубликована: Май 23, 2024
Abstract
Sterically
hindered
pyridines
embedded
in
a
three‐dimensional
triptycene
framework
have
been
synthesized,
and
their
resolution
by
chiral
HPLC
enabled
access
to
unprecedented
enantiopure
exceeding
the
known
steric
limits.
The
design
principles
for
new
axially
pyridine
derivatives
are
then
described.
To
rationalize
associations
with
Lewis
acids
transition
metals,
comprehensive
determination
of
electronic
parameters
this
class
was
performed.
This
led
general
parameterization
(percent
buried
volume
%V
Bur
,
Tolman
cone
angle
θ,
He
8
_steric
descriptor)
large
set
two‐
derivatives.
These
shown
describe
quantitatively
interactions
carbon‐
boron‐centered
were
used
predict
ΔG°
association
prototypical
B(C
6
F
5
)
3
acid
widely
frustrated
pair
catalysis.
first
sterics
is
fundamental
basis
future
development
predictive
reactivity
models
guiding
applications
bulky
organocatalysis,
pairs,
transition‐metal
Angewandte Chemie,
Год журнала:
2024,
Номер
136(45)
Опубликована: Июль 11, 2024
Abstract
Here,
we
report
a
strategy
enabling
triple
switchable
chemo‐,
regio‐,
and
stereodivergence
in
newly
developed
palladium‐catalyzed
cycloadditions
of
allenes.
An
asymmetric
pseudo‐stereodivergent
cycloaddition
allenes
bearing
primary
leaving
group
at
the
α
‐position,
where
dynamic
kinetic
hydroalkoxylation
racemic
unactivated
was
enantio‐determining
step,
is
realized,
providing
four
stereoisomers
[(
Z,R
),
(
Z,S
E,S
E,R
)]
containing
di‐substituted
alkene
scaffold
stereogenic
center.
By
tuning
reaction
conditions,
mechanistically
distinctive
uncovered
selectively
with
same
set
substrates.
switching
position
allenes,
involving
an
intermolecular
O‐attack
disclosed.
Diverse
mechanisms
reactions
enable
rapid
access
to
structurally
stereochemically
diverse
3,4‐dihydro‐2
H
‐1,4‐benzoxazines
high
efficiency
selectivity.
