Beilstein Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
21, P. 639 - 658
Published: March 20, 2025
The
transition-metal-catalyzed
asymmetric
allylic
substitution
represents
a
pivotal
methodology
in
organic
synthesis,
providing
remarkable
versatility
for
complex
molecule
construction.
Particularly,
the
generation
and
utilization
of
chiral
secondary
alkylcopper
species
have
received
considerable
attention
due
to
their
unique
properties
stereoselective
substitution.
This
review
highlights
recent
advances
copper-catalyzed
reactions
with
species,
encompassing
several
key
strategies
generation:
stereospecific
transmetalation
organolithium
organoboron
compounds,
copper
hydride
catalysis,
enantiotopic-group-selective
transformations
1,1-diborylalkanes.
Detailed
mechanistic
insights
into
stereochemical
control
current
challenges
this
field
are
also
discussed.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(23)
Published: March 9, 2022
Allylic
gem-dichlorides
are
shown
to
be
efficient
substrates
for
catalytic
asymmetric
allylboration
of
alkynes.
The
method
employs
a
chiral
NHC-Cu
catalyst
capable
generating
in
single
step
skipped
dienes
bearing
Z-alkenyl
chloride,
trisubstituted
E-alkenyl
boronate
and
bis-allylic
stereocenter
with
excellent
levels
chemo-,
regio-
enantio-
diastereoselectivity.
This
high
degree
functionalization
makes
these
products
versatile
building
blocks
as
illustrated
the
synthesis
several
optically
active
compounds.
DFT
calculations
support
key
presence
metal
cation
bridge
ligand-substrate
interaction
account
stereoselectivity
outcome.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(6), P. 3774 - 3785
Published: Feb. 1, 2023
Stereochemically
defined
trisubstituted
alkenes
with
a
bromide
and
methyl
group
at
terminus
can
be
readily
stereoretentively
derivatized
through
catalytic
cross-coupling,
affording
unsaturated
fragments
found
in
many
bioactive
natural
products.
A
direct
method
for
generating
such
entities
would
by
stereocontrolled
cross-metathesis
(CM).
Such
methods
are
scarce
however.
Here,
we
present
stereoretentive
strategy
CM
between
tri-,
Z-
or
E-di,
monosubstituted
olefins
E-2-bromo-2-butene,
an
assortment
of
E-
Z-trisubstituted
alkenyl
bromides.
The
majority
the
transformations
were
catalyzed
two
Mo
monoaryloxide
pyrrolide
(MAP)
complexes,
one
purchasable
other
accessible
well-established
protocols.
Substrates,
as
feedstock
olefins,
purchased;
reagents
commercially
available
prepared
steps
multigram
scale.
process
used
to
generate
products
that
contain
polar
moieties,
amine
alcohol,
sterically
hindered
α-
β-branched.
utility
approach
is
highlighted
brief
synthesis
fragment
phomactin
concise
total
ambrein.
An
unexpected
outcome
these
investigations
was
discovery
new
role
presence
small-molecule
alkene
olefin
metathesis
reaction.
DFT
studies
indicate
this
additive
swiftly
reacts
short-lived
alkylidene
probably
helps
circumvent
formation
catalytically
inactive
square
pyramidal
metallacyclobutanes,
enhancing
efficiency
transformation.
Applied Organometallic Chemistry,
Journal Year:
2025,
Volume and Issue:
39(3)
Published: Feb. 7, 2025
ABSTRACT
An
unprecedented
C‐SO
oxidative‐cleavage
reaction
was
disclosed
for
fused
thiazoline‐1‐oxide‐azolium
salts
with
Ag
2
O
to
afford
C
carbene
^SO
palladacyclic
complexes.
The
complex
could
undergo
reversible
redox
reactions
Br
an
intermediary
N‐heterocyclic
(NHC)
a
sulfonyl
bromide
dangling
group.
This
allowed
divergent
hydrolysis,
alcoholysis,
and
aminolysis
prepare
series
of
sulfonate
sulfonamide
functionalized
NHC
complexes
^NSO
palladacycle
via
further
deprotonation.
Selected
were
employed
in
catalysis
show
excellent
activities
the
aqueous
Suzuki‐Miyaura
coupling
hydroamination
aryl
alkynes.
Chemical Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 28, 2025
The
attractive
force
between
two
oppositely
charged
ions
can
constitute
a
powerful
design
tool
in
selective
catalysis.
Enzymes
make
extensive
use
of
ionic
interactions
alongside
variety
other
noncovalent
interactions;
recent
years
have
seen
synthetic
chemists
begin
to
seriously
explore
these
catalyst
designs
that
also
incorporate
reactive
transition
metal.
In
isolation,
single
interaction
exhibits
low
directionality,
but
many
successful
systems
they
exist
additional
which
provide
high
degree
organization
at
the
selectivity-determining
state.
Even
situations
with
key
interaction,
directionality
is
not
always
detrimental,
and
even
be
advantageous,
conferring
generality
catalyst.
This
Review
explores
approaches
utilize
control
selectivity
metal
It
divided
into
halves:
first,
occurs
outer
sphere
complex,
using
ligand
or
bound
an
anion;
second,
bears
formal
charge,
associated
counterion.
Beilstein Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
21, P. 639 - 658
Published: March 20, 2025
The
transition-metal-catalyzed
asymmetric
allylic
substitution
represents
a
pivotal
methodology
in
organic
synthesis,
providing
remarkable
versatility
for
complex
molecule
construction.
Particularly,
the
generation
and
utilization
of
chiral
secondary
alkylcopper
species
have
received
considerable
attention
due
to
their
unique
properties
stereoselective
substitution.
This
review
highlights
recent
advances
copper-catalyzed
reactions
with
species,
encompassing
several
key
strategies
generation:
stereospecific
transmetalation
organolithium
organoboron
compounds,
copper
hydride
catalysis,
enantiotopic-group-selective
transformations
1,1-diborylalkanes.
Detailed
mechanistic
insights
into
stereochemical
control
current
challenges
this
field
are
also
discussed.
