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.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(6), P. 4162 - 4184
Published: Jan. 1, 2021
This
review
provides
a
comprehensive
summary
of
recent
advances
in
nickel-catalyzed
reactions
employing
tertiary
alkyl
electrophiles
for
the
construction
quaternary
carbon
centers.
Journal of the American Chemical Society,
Journal Year:
2019,
Volume and Issue:
142(1), P. 214 - 221
Published: Dec. 15, 2019
Substantial
advances
in
enantioconvergent
C(sp3)–C(sp3)
bond
formation
reactions
have
been
made
recent
years
through
the
use
of
transition-metal-catalyzed
cross-coupling
racemic
secondary
alkyl
electrophiles
with
organometallic
reagents.
Herein,
we
report
a
general
process
for
asymmetric
construction
alkyl–alkyl
bonds
adjacent
to
heteroatoms,
namely,
nickel-catalyzed
reductive
hydroalkylation
olefins
α-heteroatom
phosphorus
or
sulfur
electrophiles.
Including
readily
available
olefins,
this
reaction
has
considerable
advantages,
such
as
mild
conditions,
broad
substrate
scope,
and
good
functional
group
compatibility,
making
it
desirable
alternative
traditional
electrophile–nucleophile
reactions.
Accounts of Chemical Research,
Journal Year:
2022,
Volume and Issue:
55(23), P. 3519 - 3536
Published: Nov. 9, 2022
Transition
metal
hydride
catalyzed
functionalization
of
remote
and
proximal
olefins
has
many
advantages
over
conventional
cross-coupling
reactions.
It
avoids
the
separate,
prior
generation
stoichiometric
amounts
organometallic
reagents
use
preformed
reagents,
which
are
sometimes
hard
to
access
may
compromise
functional
group
compatibility.
The
migratory
insertion
complexes
generated
in
situ
into
readily
available
alkene
starting
materials,
hydrometalation
process,
provides
an
attractive
straightforward
route
alkyl
intermediates,
can
undergo
a
variety
sequential
In
particular,
with
synergistic
combination
chain-walking
chemistry
nickel,
NiH-catalyzed
undergone
particularly
intense
development
past
few
years.
This
Account
aims
chronicle
progress
made
this
arena
terms
activation
modes,
diverse
functionalizations,
chemo-,
regio-,
enantioselectivity.We
first
provide
brief
introduction
general
reaction
mechanisms.
Taking
hydroarylation
as
example,
four
oxidation
states
Ni
have
allowed
us
develop
two
different
strategies
form
final
product:
Ni(I)-H/X-Ni(II)-H
platform
that
relies
on
reductants
Ni(I/II/III)
cycle
redox-neutral
or
FG-Ni(II)-H
reacts
substrate
forms
products
via
Ni(0/II)
pathway.
We
also
demonstrate
functionalization,
including
C-C
bond-forming
reactions
more
challenging
C-N/C-S
could
be
realized.
Moreover,
employment
appropriate
chiral
ligands
successfully
realize
corresponding
asymmetric
hydrofunctionalization
olefins,
hydroalkylation,
hydroarylation,
hydroalkenylation,
hydroalkynylation,
hydroamination.
Interestingly,
enantio-determining
step
enantioselective
hydronickelation,
selective
oxidative
addition,
reductive
elimination.
To
hydrofunctionalization,
we
developed
ligand
relay
catalytic
strategy
simple
ligands,
for
second
coupling.
novel
design
single,
possibly
structurally
complex
promote
both
steps
success
multicomponent
convenient
approach
gain
molecules.
Finally,
halides
used
olefin
precursors
cross-electrophile
coupling
Applications
these
discussed.
hope
will
inspire
future
field
overcome
key
challenges,
conceptually
new
strategies,
high-performance
systems
enhanced
reactivity
selectivity,
cutting-edge
catalyst
design,
further
mechanistic
studies.
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.
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(7), P. 3869 - 3874
Published: Feb. 8, 2023
Herein,
we
disclose
an
interrupted
deaminative
Ni-catalyzed
chain-walking
strategy
that
forges
sp3-sp3
architectures
at
remote,
yet
previously
unfunctionalized,
methylene
sp3
C-H
sites
enabled
by
the
presence
of
native
amides.
This
protocol
is
characterized
its
mild
conditions
and
wide
scope,
including
challenging
substrate
combinations.
Site-selectivity
can
be
dictated
a
judicious
choice
ligand,
thus
offering
opportunity
to
enable
bond
formations
are
otherwise
inaccessible
in
conventional
events.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(11), P. 4370 - 4374
Published: Jan. 7, 2020
A
modular,
site-selective
1,2-dicarbofunctionalization
of
vinyl
boronates
with
organic
halides
through
dual
catalysis
is
described.
This
reaction
proceeds
under
mild
conditions
and
characterized
by
excellent
chemo-
regioselectivity.
It
thus
represents
a
complementary
new
technique
for
preparing
densely
functionalized
alkyl
boron
architectures
from
simple
accessible
precursors.
