Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(9), P. 1796 - 1801
Published: March 2, 2022
Here,
we
report
a
nickel-catalyzed
enantioconvergent
hydroalkylation
of
olefins
with
trifluoromethyl-containing
α-alkyl
halides
for
the
synthesis
enantioenriched
trifluoromethylated
alkanes.
This
reaction
employs
readily
available
and
bench-stable
alkenes
as
alkyl
coupling
partners,
featuring
mild
conditions,
broad
substrate
scope,
high
functional
group
tolerance.
The
synthetic
utility
this
method
is
further
demonstrated
in
late-stage
functionalization
range
drug
molecules
natural
products.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(30), P. 13961 - 13972
Published: July 22, 2022
Regiodivergent
alkyne
hydroalkylation
to
generate
different
isomers
of
an
alkene
from
the
same
starting
material
would
be
beneficial;
however,
it
remains
a
challenge.
Herein,
we
report
ligand-controlled
cobalt-catalyzed
regiodivergent
hydroalkylation.
The
sensible
selection
bisoxazoline
(L1)
and
pyridine-oxazoline
(L8)
ligands
led
reliable
predictable
protocols
that
provided
(E)-1,2-disubstituted
1,1-disubstituted
alkenes
with
high
E/Z
stereoselectivity
regioisomeric
ratio
identical
terminal
alkyl
halide
substrates
produced
trisubstituted
in
case
internal
alkynes.
This
method
exhibits
broad
scope
for
alkynes
wide
range
activated
unactivated
halides
shows
excellent
functional
group
compatibility.
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).
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.
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.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(31)
Published: May 25, 2022
Regiodivergent
alkene
functionalization
that
produces
either
regioisomer
starting
from
the
same
raw
materials
is
desirable.
Herein,
we
report
a
nickel-catalyzed
switchable
site-selective
hydroalkylation.
The
selection
of
reaction
temperatures
leads
to
protocols
provide
regiodivergent
hydroalkylated
products
single
substrate.
This
protocol
allows
convenient
synthesis
α-
and
β-branched
protected
amines,
both
which
are
important
fields
pharmaceutical
chemistry
biochemistry.
In
addition,
enantioenriched
alkylamines
can
be
accessed
in
catalytic
asymmetric
variant.
Preliminary
mechanistic
studies
indicate
formation
more
stable
nickelacycle
provides
driving
force
migration.
thermodynamic
kinetic
properties
different
reduction
elimination
intermediates
responsible
for
site-selectivity.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(14), P. 8766 - 8773
Published: July 2, 2021
Here,
we
report
an
enantioselective
nickel-hydride
catalyzed
hydroalkylation
of
readily
accessible
β-alkyl-α,β-unsaturated
amides
to
form
structurally
diverse
β-chiral
amides.
This
process
was
proposed
proceed
through
enantiodifferentiating
syn-hydrometalation
nickel
hydride,
forming
chiral
alkylnickel
at
the
β-position
in
which
regioselectivity
is
different
from
that
with
copper
hydride.
regio-reversed
hydronickellation
provides
a
complementary
approach
access
enantioenriched
β-functionalization
stereocenter
β-position.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: April 7, 2022
Abstract
Alkene
hydrocarbonation
reactions
have
been
developed
to
supplement
traditional
electrophile-nucleophile
cross-coupling
reactions.
The
branch-selective
hydroalkylation
method
applied
a
broad
range
of
unactivated
alkenes
remains
challenging.
Herein,
we
report
NiH-catalysed
proximal-selective
access
β-
or
γ-branched
alkyl
carboxylic
acids
and
β-,
γ-
δ-branched
amines.
A
iodides
bromides
with
different
functional
groups
can
be
installed
excellent
regiocontrol
availability
for
site-selective
late-stage
functionalization
biorelevant
molecules.
Under
modified
reaction
conditions
NiCl
2
(PPh
3
)
as
the
catalyst,
migratory
takes
place
provide
(rather
than
γ-)
branched
products.
keys
success
are
use
aminoquinoline
picolinamide
suitable
directing
combined
experimental
computational
studies
ligand
effects
on
regioselectivity
detailed
mechanisms.
