Chinese Journal of Chemistry,
Journal Year:
2022,
Volume and Issue:
40(13), P. 1608 - 1622
Published: April 3, 2022
Comprehensive
Summary
“Chain‐walking”
reactions
could
realize
to
modify
a
molecule
at
the
position
far
away
from
active
site.
It
has
been
hot
topic
in
research
field
of
organic
synthesis.
As
number
achievements
have
made
by
researchers,
products
transition
metal‐catalyzed
chain‐walking
be
obtained
with
good
enantioselectivity.
This
review
summarized
researches
on
asymmetric
catalyzed
metal
past
decade.
These
works
are
classified
according
species
catalysts.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
60(4), P. 1883 - 1890
Published: Oct. 6, 2020
Abstract
A
regiodivergent
nickel‐catalyzed
hydrocyanation
of
a
broad
range
internal
alkenes
involving
chain‐walking
process
is
reported.
When
appropriate
diastereomeric
biaryl
diphosphite
ligands
are
applied,
the
same
starting
materials
can
be
converted
to
either
linear
or
branched
nitriles
with
good
yields
and
high
regioselectivities.
DFT
calculations
suggested
that
catalyst
architecture
determines
regioselectivity
by
modulating
electronic
steric
interactions.
In
addition,
moderate
enantioselectivities
were
observed
when
produced.
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: Sept. 24, 2021
Transition
metal-catalyzed
asymmetric
allylic
substitution
with
a
suitably
pre-stored
leaving
group
in
the
substrate
is
widely
used
organic
synthesis.
In
contrast,
enantioselective
C(sp3)-H
functionalization
more
straightforward
but
far
less
explored.
Here
we
report
catalytic
protocol
for
long-standing
challenging
functionalization.
Through
palladium
hydride-catalyzed
chain-walking
and
substitution,
C-H
of
wide
range
acyclic
nonconjugated
dienes
achieved
high
yields
(up
to
93%
yield),
enantioselectivities
98:2
er),
100%
atom
efficiency.
Exploring
reactivity
substrates
varying
pKa
values
uncovers
reasonable
scope
nucleophiles
potential
factors
controlling
reaction.
A
set
efficient
downstream
transformations
enantiopure
skeletons
showcase
practical
value
methodology.
Mechanistic
experiments
corroborate
PdH-catalyzed
migratory
process.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(23)
Published: March 17, 2022
Abstract
A
remote
C(sp
3
)−H
bond
asymmetric
borylation
of
unactivated
alkenes
was
achieved
by
bimetallic
relay
catalysis.
The
reaction
proceeded
through
reversible
and
consecutive
β‐H
elimination/olefin
insertion
promoted
CoH
species
generated
in
situ,
followed
copper‐catalyzed
protoboration.
use
this
synergistic
Co/Cu
catalysis
protocol
allowed
the
enantioselective
protoboration
various
terminal
internal
alkenes,
as
well
an
unrefined
mixture
olefin
isomers,
at
distal
less‐reactive
β‐position
to
a
functional
group,
leading
chiral
organoboronates.
Chinese Journal of Chemistry,
Journal Year:
2022,
Volume and Issue:
40(13), P. 1608 - 1622
Published: April 3, 2022
Comprehensive
Summary
“Chain‐walking”
reactions
could
realize
to
modify
a
molecule
at
the
position
far
away
from
active
site.
It
has
been
hot
topic
in
research
field
of
organic
synthesis.
As
number
achievements
have
made
by
researchers,
products
transition
metal‐catalyzed
chain‐walking
be
obtained
with
good
enantioselectivity.
This
review
summarized
researches
on
asymmetric
catalyzed
metal
past
decade.
These
works
are
classified
according
species
catalysts.
