Journal of the American Chemical Society,
Год журнала:
2019,
Номер
141(12), С. 5034 - 5044
Опубликована: Март 2, 2019
The
synthesis
and
spectroscopic
characterization
of
a
family
Ni–X
(X
=
Cl,
Br,
I,
H)
complexes
supported
by
the
bulky
α-diimine
chelate
N,N′-bis(1R,2R,3R,5S)-(−)-isopinocampheyl-2,3-butanediimine
(ipcADI)
are
described.
Diimine-supported,
three-coordinate
nickel(I)–X
have
been
proposed
as
key
intermediates
in
host
catalytic
transformations
such
C–C
C–heteroatom
cross-coupling
C–H
functionalization
but
until
now
remained
synthetically
elusive.
A
combination
structural,
spectroscopic,
electrochemical,
computational
studies
were
used
to
establish
electronic
structure
each
monomeric
[(ipcADI)NiX]
I)
complex
nickel(I)
derivative
redox-neutral
chelate.
dimeric
nickel
hydride,
[(ipcADI)Ni(μ2-H)]2,
was
prepared
characterized
X-ray
diffraction;
however,
magnetic
measurements
1H
NMR
spectroscopy
support
monomer
formation
at
ambient
temperature
THF
solution.
This
hydride
precatalyst
for
hydrogen
isotope
exchange
(HIE)
bonds
arenes
pharmaceuticals.
By
virtue
multisite
reactivity
high
efficiency,
new
provided
unprecedented
specific
activities
(50–99
Ci/mmol)
radiolabeling,
meeting
threshold
required
radioligand
binding
assays.
Use
air-stable
readily
synthesized
precursor,
[(ipcADI)NiBr2],
broad
functional
group
tolerance,
compatibility
with
polar
protic
solvents
additional
assets
nickel-catalyzed
HIE
method.
Journal of the American Chemical Society,
Год журнала:
2019,
Номер
141(44), С. 17937 - 17948
Опубликована: Окт. 7, 2019
Ni-catalyzed
cross-electrophile
coupling
reactions
have
emerged
as
appealing
methods
to
construct
organic
molecules
without
the
use
of
stoichiometric
organometallic
reagents.
The
mechanisms
are
complex:
plausible
pathways,
such
"radical
chain"
and
"sequential
reduction"
mechanisms,
dependent
on
sequence
activation
electrophiles.
A
combination
kinetic,
spectroscopic,
studies
reveals
that
a
Ni-catalyzed,
reductive
1,2-dicarbofunctionalization
alkenes
proceeds
through
pathway.
reduction
Ni
by
Zn
is
turnover-limiting
step,
consistent
with
Ni(II)
intermediates
catalyst
resting-state.
only
sufficient
reduce
(phen)Ni(II)
Ni(I)
species.
As
result,
commonly
proposed
Ni(0)
absent
under
these
conditions.
(Phen)Ni(I)–Br
selectively
activates
aryl
bromides
via
two-electron
oxidation
addition,
whereas
alkyl
activated
(phen)Ni(I)–Ar
single-electron
afford
radicals.
These
findings
could
provide
insight
into
achieving
selectivity
between
different
Journal of the American Chemical Society,
Год журнала:
2019,
Номер
141(41), С. 16197 - 16201
Опубликована: Сен. 29, 2019
A
catalytic
deaminative
alkylation
of
unactivated
olefins
is
described.
The
protocol
characterized
by
its
mild
conditions,
wide
scope,
including
the
use
ethylene
as
substrate,
and
exquisite
site-selectivity
pattern
for
both
α-olefins
internal
olefins,
thus
unlocking
a
new
platform
to
forge
sp3-sp3
linkages,
even
in
context
late-stage
functionalization.
Angewandte Chemie International Edition,
Год журнала:
2018,
Номер
58(6), С. 1754 - 1758
Опубликована: Дек. 12, 2018
Reported
here
is
a
terminal-selective,
remote
asymmetric
hydroalkylation
of
olefins
with
racemic
α-bromo
amides.
The
reaction
proceeds
by
NiH-catalyzed
alkene
isomerization
and
subsequent
alkylation
reaction,
can
enantioconvergently
introduce
an
unsymmetrical
secondary
alkyl
group
from
amide
onto
terminal
C(sp3
)-H
position
along
the
hydrocarbon
chain
alkene.
This
mild
process
affords
range
structurally
diverse
chiral
α-alkylalkanoic
amides
in
excellent
yields,
high
regio-
enantioselectivities.
In
addition,
synthetic
utility
this
protocol
further
highlighted
regioconvergent
conversion
industrial
raw
materials
isomeric
olefin
mixtures
into
enantioriched
on
large
scale.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
59(16), С. 6520 - 6524
Опубликована: Дек. 3, 2019
A
highly
regioselective
Ni-catalyzed
electrochemical
reductive
relay
cross-coupling
between
an
aryl
halide
and
alkyl
has
been
developed
in
undivided
cell.
Various
functional
groups
are
tolerated
under
these
mild
reaction
conditions,
which
provides
alternative
approach
for
the
synthesis
of
1,1-diarylalkanes.
Israel Journal of Chemistry,
Год журнала:
2019,
Номер
60(3-4), С. 195 - 206
Опубликована: Авг. 21, 2019
Abstract
Nickel
catalysts
have
recently
played
an
important
role
for
rapidly
and
reliably
converting
feedstock
chemicals
into
valuable
compounds
of
interest
both
pharmaceutical
academic
laboratories.
Herein,
we
summarize
the
recent
advances
on
ability
nickel
to
trigger
olefin
isomerization
via
“chain‐walking”,
causing
a
displacement
catalyst
throughout
alkyl
chain
while
opening
up
new
grounds
forging
C−C
C‐heteroatom
linkages
at
remote,
yet
unfunctionalized,
sp
3
C−H
bonds.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(6), С. 4162 - 4184
Опубликована: Янв. 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,
Год журнала:
2019,
Номер
142(1), С. 214 - 221
Опубликована: Дек. 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.
Journal of the American Chemical Society,
Год журнала:
2019,
Номер
141(19), С. 7709 - 7714
Опубликована: Апрель 29, 2019
Metal-hydride
hydrogen
atom
transfer
(MHAT)
functionalizes
alkenes
with
predictable
branched
(Markovnikov)
selectivity.
The
breadth
of
these
transformations
has
been
confined
to
π-radical
traps;
no
sp3
electrophiles
have
reported.
Here
we
describe
a
Mn/Ni
dual
catalytic
system
that
hydroalkylates
unactivated
olefins
alkyl
halides,
yielding
aliphatic
quaternary
carbons.
