Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(46), P. 25293 - 25303
Published: Nov. 8, 2023
Catalytic
carboamination
of
alkenes
is
a
powerful
synthetic
tool
to
access
valuable
amine
scaffolds
from
abundant
and
readily
available
alkenes.
Although
number
approaches
have
been
developed
achieve
the
rapid
buildup
molecular
complexity
in
this
realm,
installation
diverse
carbon
nitrogen
functionalities
onto
unactivated
remains
underdeveloped.
Here
we
present
ligand
design
approach
enable
nickel-catalyzed
three-component
carboamidation
that
applicable
wide
range
alkenyl
derivatives
via
tandem
process
involving
alkyl
migratory
insertion
inner-sphere
metal-nitrenoid
transfer.
With
method,
various
can
be
installed
into
both
internal
terminal
alkenes,
leading
differentially
substituted
diamines
would
otherwise
difficult
access.
Mechanistic
investigations
reveal
tailored
Ni(cod)(BQiPr)
precatalyst
modulates
electronic
properties
presumed
π-alkene-nickel
intermediate
quinone
ligand,
enhanced
carbonickelation
efficiency
across
C═C
bond.
These
findings
establish
nickel's
ability
catalyze
multicomponent
with
high
exquisite
selectivity.
Inorganics,
Journal Year:
2025,
Volume and Issue:
13(2), P. 41 - 41
Published: Feb. 1, 2025
Six
N^C^N
cyclometalated
Ni(II)
complexes
[Ni(N^C^N)Cl]
or
[Ni(N^C^N’)Br]
with
symmetric
non-symmetric
N^C^N’
ligands
in
which
the
peripheral
N-groups
were
varied
pyridine
(Py),
4-thiazole
(4Tz),
2-thiazole
(2Tz),
and
2-benzothiazole
(2Btz)
complementing
previously
reported
di(2-pyridyl)phenide
[Ni(Py(Ph)Py)X]
X
=
Cl
Br.
The
synthesized
from
NiBr2
N^CH^N’
protoligands
through
base-assisted
nickelation,
while
received
N^C(Cl)^N
[Ni(COD)2]
(COD
1,5-cyclooctadiene).
Introduction
of
4Tz
on
both
sides
shifted
electrochemical
gap
ΔEexp
Eox–Ered
long
wavelength
UV-vis
absorption
maxima
to
higher
energies,
2Tz
leads
a
shift
lower
energies.
When
introducing
only
one
as
groups,
remaining
PhPy
moiety
dominates
electronic
properties
electrochemistry
photophysics
are
very
similar
Py(Ph)Py
derivatives.
In
contrast
this,
introduction
2Btz
shifts
values
regardless
two
groups
character
frontier
molecular
orbitals
complexes,
DFT
calculations
show.
Long-wavelength
absorptions
vary
416
443
nm,
their
energies
correlate
well
first
reduction
potentials.
Negishi-type
C–C
cross-coupling
reactions
gave
total
yields
ranging
1
60%
44%.
reactivities
roughly
Facilitated
(E
around
–2
higher)
goes
generally
along
improved
performance,
making
thiazole-containing
interesting
candidates
for
such
catalysis.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(46), P. 25293 - 25303
Published: Nov. 8, 2023
Catalytic
carboamination
of
alkenes
is
a
powerful
synthetic
tool
to
access
valuable
amine
scaffolds
from
abundant
and
readily
available
alkenes.
Although
number
approaches
have
been
developed
achieve
the
rapid
buildup
molecular
complexity
in
this
realm,
installation
diverse
carbon
nitrogen
functionalities
onto
unactivated
remains
underdeveloped.
Here
we
present
ligand
design
approach
enable
nickel-catalyzed
three-component
carboamidation
that
applicable
wide
range
alkenyl
derivatives
via
tandem
process
involving
alkyl
migratory
insertion
inner-sphere
metal-nitrenoid
transfer.
With
method,
various
can
be
installed
into
both
internal
terminal
alkenes,
leading
differentially
substituted
diamines
would
otherwise
difficult
access.
Mechanistic
investigations
reveal
tailored
Ni(cod)(BQiPr)
precatalyst
modulates
electronic
properties
presumed
π-alkene-nickel
intermediate
quinone
ligand,
enhanced
carbonickelation
efficiency
across
C═C
bond.
These
findings
establish
nickel's
ability
catalyze
multicomponent
with
high
exquisite
selectivity.
