ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
13(1), P. 744 - 748
Published: Dec. 23, 2022
Herein,
we
report
a
cobalt-catalyzed
asymmetric
reductive
1,2-dicarbofunctionalization
of
1,3-dienes
employing
o-bromoaryl
imines
as
bis-electrophilic
coupling
partner.
This
method
provides
an
entry
to
prepare
disubstituted
cis-indanes
in
high
diastereo-
and
enantioselectivities
under
mild
reaction
conditions.
The
proposed
mechanism
consists
enantioselective
intermolecular
migratory
insertion
diastereoselective
intramolecular
allylation
the
key
elementary
steps.
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(15), P. 8237 - 8246
Published: June 24, 2020
Nickel-catalyzed
reductive
cross-coupling
reactions
have
emerged
as
powerful
methods
to
join
two
electrophiles.
These
proven
particularly
useful
for
the
coupling
of
sec-alkyl
electrophiles
form
stereogenic
centers;
however,
development
enantioselective
variants
remains
challenging.
In
this
Perspective,
we
summarize
progress
that
has
been
made
toward
Ni-catalyzed
reactions.
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(15), P. 8542 - 8556
Published: July 2, 2020
1,2-Dicarbofunctionalization
of
alkenes
has
emerged
as
an
efficient
synthetic
strategy
for
preparing
substituted
molecules
by
coupling
readily
available
with
electrophiles
and/or
nucleophiles.
Nickel
complexes
serve
effective
catalysts
owing
to
their
tendency
undergo
facile
oxidative
addition
and
slow
β-hydride
elimination,
capability
access
both
two-electron
radical
pathways.
Two-component
alkene
functionalization
reactions
have
achieved
high
chemo-,
regio-,
stereoselectivities
tethering
one
the
partners
substrate.
Three-component
reactions,
however,
often
incorporate
directing
groups
control
selectivity.
Only
a
few
examples
directing-group-free
difunctionalizations
unactivated
been
reported.
Therefore,
great
opportunities
exist
development
three-component
difunctionalization
broad
substrate
scopes
tunable
stereoselectivities.
Chinese Journal of Chemistry,
Journal Year:
2020,
Volume and Issue:
38(11), P. 1371 - 1394
Published: June 16, 2020
As
a
straightforward
strategy
for
rapidly
increasing
molecular
complexity,
dicarbofunctionalization
of
alkenes
has
attracted
substantial
interests
organic
synthesis,
medicine
chemistry,
and
materials
science.
Nickel‐catalyzed
cascade
dicarbofunctionalizations
have
been
flourished
in
this
area
recently,
nickel‐mediated
radical
pathways
particularly
offer
new
opportunities
conjunctive
cross‐couplings
with
alkyl
coupling
partners.
Herein,
we
give
comprehensive
review
nickel‐catalyzed
through
historical
perspective,
including
intermolecular
three‐component
reactions
intramolecular
reactions.
Among
the
discussed
review,
carbometallation/cross‐coupling
process
addition/cross‐coupling
are
two
major
alkenes.
The
oxidative
cyclization
1,2‐metallate
shift
processes
also
selectively
discussed.
These
methods
overcome
limitations
associated
using
noble
metals
field,
providing
an
efficient
access
to
structurally
diversified
molecules.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(44), P. 23910 - 23917
Published: Oct. 26, 2023
The
merger
of
electrochemistry
and
transition
metal
catalysis
has
emerged
as
a
powerful
tool
to
join
two
electrophiles
in
an
enantioselective
manner.
However,
the
development
electroreductive
cross-couplings
olefins
remains
challenge.
Inspired
by
advantages
synergistic
use
with
nickel
catalysis,
we
present
here
Ni-catalyzed
cross-coupling
acrylates
aryl
halides
alkyl
bromides,
which
affords
chiral
α-aryl
carbonyls
good
excellent
enantioselectivity.
Additionally,
this
catalytic
reaction
can
be
applied
(hetero)aryl
chlorides,
is
difficult
achieve
other
methods.
combination
cyclic
voltammetry
analysis
electrode
potential
studies
suggests
that
NiI
species
activates
oxidative
addition
bromides
single-electron
transfer.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 26, 2024
Cross-electrophile
coupling
(XEC),
defined
by
us
as
the
cross-coupling
of
two
different
σ-electrophiles
that
is
driven
catalyst
reduction,
has
seen
rapid
progression
in
recent
years.
As
such,
this
review
aims
to
summarize
field
from
its
beginnings
up
until
mid-2023
and
provide
comprehensive
coverage
on
synthetic
methods
current
state
mechanistic
understanding.
Chapters
are
split
type
bond
formed,
which
include
C(sp
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(42), P. 19337 - 19343
Published: Oct. 12, 2022
An
asymmetric
1,2-dicarbofunctionalization
of
unactivated
alkenes
with
aryl
iodides
and
aryl/alkenylboronic
esters
under
nickel/bioxazoline
catalysis
is
disclosed.
A
wide
array
alkenyl
nucleophiles
are
tolerated,
furnishing
the
products
in
good
yield
high
enantioselectivity.
In
addition
to
terminal
alkenes,
1,2-disubstituted
internal
participate
reaction,
establishing
two
contiguous
stereocenters
diastereoselectivity
moderate
combination
experimental
computational
techniques
shed
light
on
mechanism
catalytic
transformation,
pointing
a
closed-shell
pathway
an
enantiodetermining
migratory
insertion
step,
where
stereoinduction
arises
from
synergistic
interactions
between
sterically
bulky
achiral
sulfonamide
directing
group
hemilabile
bidentate
ligand.
Synthesis,
Journal Year:
2023,
Volume and Issue:
56(01), P. 1 - 15
Published: June 12, 2023
Abstract
Catalytic
enantioselective
1,2-dicarbofunctionalization
(1,2-DCF)
of
alkenes
is
a
powerful
transformation
growing
importance
in
organic
synthesis
for
constructing
chiral
building
blocks,
bioactive
molecules,
and
agrochemicals.
Both
two-
three-component
context,
this
family
reactions
generates
densely
functionalized,
structurally
complex
products
single
step.
Across
several
distinct
mechanistic
pathways
at
play
these
transformations
with
nickel
or
palladium
catalysts,
stereocontrol
can
be
obtained
through
tailored
ligands.
In
Review
we
discuss
the
various
strategies,
mechanisms,
catalysts
that
have
been
applied
to
achieve
enantioinduction
alkene
1,2-DCF.
1
Introduction
2
Two-Component
Enantioselective
1,2-DCF
via
Migratory
Insertion
3
Radical
Capture
4
Three-Component
5
6
Miscellaneous
Mechanisms
7
Conclusion
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(7), P. 4395 - 4406
Published: March 8, 2024
Asymmetric
reductive
three-component
arylalkylation
of
alkenes
via
the
radical
relay
method
has
been
well
established,
while
asymmetric
migratory
insertion
strategy
remains
unexplored.
We
report
enantioselective
nickel-catalyzed
cross-electrophile
with
aryl-
and
alkyl
halides
an
integrated
Heck
carbometalation/radical
cross-coupling
sequence.
This
protocol
employing
a
chiral
Ni/PHOX
catalytic
system
allows
terminal
internal
to
successfully
engage
exquisite
control
regio-,
chemo-,
stereoselectivity.
More
importantly,
this
undergoes
regio-
arylnickelation
followed
by
Csp3–Csp3
elimination,
thus
exhibiting
reverse
regioselectivity
method.
Mild
reaction
conditions
exceptional
functional
group
tolerance
facilitate
method's
compatibility
bioactive
motifs
modular
synthesis
biologically
active
compounds.
The
experiments
density
theory
calculations
provide
insights
into
mechanism
origin
stereoselectivity,
hemilabile
nature
PHOX
ligand
is
critical
for
achieving
arylalkylation.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(47), P. 19844 - 19849
Published: Nov. 10, 2020
A
carbamoyl
fluoride-enabled
enantioselective
Ni-catalyzed
carbocarbamoylation
of
unactivated
alkenes
was
developed,
providing
a
broad
range
chiral
γ-lactams
bearing
an
all-carbon
quaternary
center
in
45–96%
yield
and
38–97%
ee.
