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.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(11), P. 4168 - 4173
Published: March 11, 2021
1,3-Dienes
are
readily
available
feedstocks
that
widely
used
in
the
laboratory
and
industry.
However,
potential
of
converting
1,3-dienes
into
value-added
products,
especially
chiral
has
not
yet
been
fully
exploited.
By
synergetic
photoredox/copper
catalysis,
we
achieve
first
visible-light-induced,
enantioselective
carbocyanation
by
using
carboxylic
acid
derivatives
trimethylsilyl
cyanide.
Under
mild
neutral
conditions,
a
diverse
range
allyl
cyanides
produced
generally
good
efficiency
with
high
enantioselectivity
from
bench-stable
user-safe
chemicals.
Moreover,
preliminary
results
also
confirm
this
success
can
be
expanded
to
1,3-enynes
four-component
carbonylative
1,3-enynes.
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: Jan. 27, 2021
Enantiomerically
pure
chiral
amines
and
related
amide
derivatives
are
privilege
motifs
in
many
pharmacologically
active
molecules.
In
comparison
to
the
well-established
hydroamination,
transition
metal-catalysed
asymmetric
hydrofunctionalization
of
enamines
provides
a
complementary
approach
for
their
construction.
Here
we
report
NiH-catalysed
enantio-
regioselective
reductive
hydroarylation
N-acyl
enamines,
allowing
practical
access
broad
range
structurally
diverse,
enantioenriched
benzylamines
under
mild,
operationally
simple
reaction
conditions.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(18), P. 10411 - 10421
Published: April 26, 2023
Site-
and
enantio-selective
alkyl-alkyl
bond
formation
is
privileged
in
the
retrosynthetic
analysis
due
to
universality
of
sp3-hybridized
carbon
atoms
organic
molecules.
Herein,
we
report
a
nickel-catalyzed
remote
asymmetric
hydroalkylation
alkenyl
ethers
via
synchronous
implementation
alkene
isomerization
enantioselective
C(sp3)-C(sp3)
formation.
Regression
catalyst
structure-activity
relationships
accelerates
rational
ligand
modification
through
modular
regulation.
This
reaction
has
several
advantages
for
synthesizing
chiral
dialkyl
carbinols
their
ether
derivatives,
including
broad
substrate
scope,
good
functional
group
tolerance,
excellent
regioselectivity
(>20:1
regioisomeric
ratio),
high
enantioselectivity
(up
95%
enantiomeric
excess).
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(2), P. 1410 - 1422
Published: Jan. 5, 2024
Alkene
radical
ions
constitute
an
integral
and
unique
class
of
reactive
intermediates
for
the
synthesis
valuable
compounds
because
they
have
both
unpaired
spins
charge.
However,
relatively
few
synthetic
applications
alkene
anions
emerged
due
to
a
dearth
generally
applicable
mild
anion
generation
approaches.
Precise
control
over
chemo-
stereoselectivity
in
anion-mediated
processes
represents
another
long-standing
challenge
their
high
reactivity.
To
overcome
these
issues,
here,
we
develop
new
redox-neutral
strategy
that
seamlessly
merges
photoredox
copper
catalysis
enable
controlled
orthogonal
enantioselective
cyanofunctionalization
via
distonic-like
species.
This
enables
highly
regio-,
chemo-,
hydrocyanation,
deuterocyanation,
cyanocarboxylation
alkenes
without
stoichiometric
reductants
or
oxidants
under
visible
light
irradiation.
protocol
provides
blueprint
exploration
transformation
potential
anions.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(35), P. 14089 - 14096
Published: Aug. 26, 2021
A
nickel-catalyzed,
multicomponent
regio-
and
enantioselective
coupling
via
sequential
hydroformylation
carbonylation
from
readily
available
starting
materials
has
been
developed.
This
modular
hydrofunctionalization
strategy
enables
the
straightforward
reductive
hydrocarbonylation
of
a
broad
range
unactivated
alkenes
to
produce
wide
variety
unsymmetrical
dialkyl
ketones
bearing
functionalized
α-stereocenter,
including
enantioenriched
chiral
α-aryl
α-amino
ketones.
It
uses
bisoxazoline
as
ligand,
silane
reductant,
chloroformate
safe
CO
source,
racemic
secondary
benzyl
chloride
or
an
N-hydroxyphthalimide
(NHP)
ester
protected
acid
alkylation
reagent.
The
benign
nature
this
process
renders
method
suitable
for
late-stage
functionalization
complex
molecules.
Chinese Journal of Chemistry,
Journal Year:
2021,
Volume and Issue:
40(5), P. 651 - 661
Published: Dec. 3, 2021
Comprehensive
Summary
Enantioselective
NiH‐catalyzed
reductive
hydrofunctionalization
of
olefins
has
attracted
much
attention
in
recent
years.
Using
simple
chiral
ligands,
a
wide
array
functionalized
and
electrophiles
can
undergo
diverse
transformations
to
afford
hydrofunctionalized
products,
regio‐
enantioselectively.
These
processes
avoid
the
prior
preparation
organometallic
reagents,
construct
stereogenic
center
at
carbon
originating
either
from
olefin
or
electrophile.
This
review
discusses
background,
major
progress
mechanistic
investigations
this
reaction.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(37), P. 14962 - 14968
Published: Sept. 8, 2021
A
NiH-catalyzed
thioether-directed
cyclometalation
strategy
is
developed
to
enable
remote
methylene
C–H
bond
amidation
of
unactivated
alkenes.
Due
the
preference
for
five-membered
nickelacycle
formation,
chain-walking
isomerization
initiated
by
NiH
insertion
an
alkene
can
be
terminated
at
γ-methylene
site
from
moiety.
By
employing
2,9-dibutyl-1,10-phenanthroline
(L4)
as
ligand
and
dioxazolones
reagent,
occurs
γ-C(sp3)–H
bonds
afford
amide
products
in
up
90%
yield
(>40
examples)
with
remarkable
regioselectivity
(up
24:1
rr).
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(44), P. 23584 - 23589
Published: Aug. 27, 2021
Regio-
and
enantioselective
hydroarylamination,
hydroalkylamination
hydroamidation
of
styrenes
have
been
developed
by
NiH
catalysis
with
a
simple
bioxazoline
ligand
under
mild
conditions.
A
wide
range
enantioenriched
benzylic
arylamines,
alkylamines
amides
can
be
easily
accessed
nitroarenes,
hydroxylamines
dioxazolones,
respectively
as
amination
reagents.
The
chiral
induction
in
these
reactions
is
proposed
to
proceed
through
an
enantiodifferentiating
syn-hydronickellation
step.
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: Sept. 27, 2021
Abstract
Remote
functionalization
of
alkenes
via
chain
walking
has
generally
been
limited
to
C(sp
3
)–H
bonds
α
and
β
polar-functional
units,
while
γ
-C(sp
through
controlled
alkene
transposition
is
a
longstanding
challenge.
Herein,
we
describe
NiH-catalyzed
migratory
formal
hydroamination
alkenyl
amides
achieved
chelation-assisted
control,
whereby
various
amino
groups
are
installed
at
the
-position
aliphatic
chains.
By
tuning
olefin
isomerization
ligand
directing
group
optimization,
-selective
amination
can
be
stabilization
6-membered
nickellacycle
by
an
8-aminoquinoline
subsequent
interception
aminating
reagent.
A
range
amines
bond
unactivated
with
varying
alkyl
lengths,
enabling
late-stage
access
value-added
-aminated
products.
Moreover,
employing
picolinamide-coupled
substrates,
this
approach
further
extended
δ
amination.
The
chain-walking
mechanism
pathway
selectivity
investigated
experimental
computational
methods.
