Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(13), P. 9375 - 9384
Published: March 21, 2024
Catalytic
formation
of
a
regio-
and
enantioselective
C–F
bond
chiral
center
from
readily
available
alkenes
is
crucial
goal,
yet
it
continues
to
pose
significant
challenges
in
organic
synthesis.
Here,
we
report
the
regioselective
bonds
facilitated
by
NiH
catalysis
coordination
directing
strategy
that
enables
precise
hydrofluorination
both
terminal
internal
alkenes.
Notably,
have
optimized
this
methodology
achieve
high
enantioselectivity
creating
aliphatic
stereogenic
centers
especially
with
β,γ-alkenyl
substrates,
using
tailored
Bn-BOx
ligand.
Another
pivotal
finding
our
research
identification
(+)-nonlinear
effect
under
conditions,
allowing
for
even
moderately
enantiomerically
enriched
ligands.
Given
role
fluorine
pharmaceuticals
synthetic
materials,
offers
essential
insights
into
centers,
paving
way
efficient
production
valuable
fluorinated
compounds.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(16), P. 7015 - 7029
Published: April 12, 2022
Compounds
rich
in
sp3-hybridized
carbons
are
desirable
drug
discovery.
Nickel-catalyzed
hydrocarbonation
of
alkenes
is
a
potentially
efficient
method
to
synthesize
these
compounds.
By
using
abundant,
readily
available,
and
stable
as
pro-nucleophiles,
reactions
can
have
broad
scope
high
functional
group
tolerance.
However,
this
methodology
still
an
early
stage
development,
the
first
examples
were
reported
only
2016.
Herein,
we
summarize
progress
emerging
field,
with
emphasis
on
enantioselective
reactions.
We
highlight
major
developments,
critically
discuss
wide
range
possible
mechanisms,
offer
our
perspective
state
challenges
field.
hope
Perspective
will
stimulate
future
works
area,
making
widely
applicable
organic
synthesis.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(14), P. 7983 - 7991
Published: March 28, 2023
Conjugate
addition
is
among
the
most
important
synthetic
protocols
for
constructing
carbon
skeletons
and
widely
used
to
synthesize
natural
products
drugs.
However,
asymmetric
catalysis
studies
have
mainly
focused
on
stereogenic
centers
arising
from
conjugate
alkenes.
Here,
we
report
first
photoinduced
cobalt-catalyzed
dynamic
kinetic
reductive
reaction
that
enables
formation
of
heterobiaryls
with
axial
chirality
(45
examples,
up
91%
yield
97%
ee).
This
method
features
mild
conditions,
good
functional-group
tolerance,
excellent
enantiomeric
control.
Significantly,
large
amounts
metal
waste
precious
catalysts
can
be
avoided
under
these
conditions.
Migration
chiral
arylcobalt
species
into
alkene
might
rate-determining
step
based
studies.
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(28), P. 18892 - 18898
Published: July 5, 2024
Herein,
we
designed
a
reaction
for
the
desymmetrization-addition
of
cyclopropenes
to
imines
by
leveraging
synergy
between
photoredox
and
asymmetric
cobalt
catalysis.
This
protocol
facilitated
synthesis
series
chiral
functionalized
cyclopropanes
with
high
yield,
enantioselectivity,
diastereoselectivity
(44
examples,
up
93%
yield
>99%
ee).
A
possible
mechanism
involving
cyclopropene
desymmetrization
Co-H
species
imine
addition
Co-alkyl
was
proposed.
study
provides
novel
route
important
extends
frontier
metallaphotoredox
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.
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.
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.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(15), P. 9779 - 9789
Published: July 27, 2022
A
Ni-catalyzed
enantioselective
reductive
three-component
alkylalkenylation
of
β,γ-alkenyl
ketones
with
cis-alkenyl
iodides
and
fluoroalkyl
in
the
presence
Mn
is
reported.
By
leveraging
five-membered
nickellacycles
stabilized
by
pendant
ketone
group
chiral
bis(oxazoline)
(BiOx)
ligand,
this
protocol
allows
efficient
access
to
enantioenriched
β-alkenyl
from
simple
starting
materials.
diverse
electronically
unbiased
alkenes
beyond
that
enables
regioselective
construction
two
C(sp3)–C(sp3)
C(sp3)–(sp2)
bonds
one
single
operation
also
demonstrated.
