Chemistry - An Asian Journal,
Journal Year:
2020,
Volume and Issue:
15(20), P. 3209 - 3224
Published: Aug. 14, 2020
In
2005,
a
facile
dihydrogen
activation
was
reported
by
the
Power
group
using
an
alkyne
analog
of
germanium
[ArGe≡GeAr;
Ar=2,6-Trip2
-C6
H3
(Trip=2,4,6-i
Pr3
H2
)].
After
that,
significant
progress
has
been
made
in
various
small
molecules
main-group
compounds,
and
variety
stoichiometric
catalytic
processes
have
formulated
p-block
elements.
this
regard,
compounds
containing
low-valent
elements
with
frontier
orbitals
relatively
energy
gaps
or
forming
frustrated
Lewis
pair
(FLP)
became
quite
successful.
spite
these
promising
transformations,
redox-cycling
catalysts
based
on
remain
extremely
rare.
Recently,
it
observed
that
pincer
type
ligands
supported
geometry
constrained
are
capable
acting
as
redox
similar
to
those
transition
metals.
review,
we
focus
synthesis
structural
aspects
ligands.
Emphasis
placed
their
applications
activity
activation.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(20), P. 8902 - 8907
Published: May 12, 2022
A
catalytic
approach
to
intercept
the
transient
HNO
for
a
chemoselective
primary
amination
of
arylboronic
acids
is
reported.
phosphetane-based
catalyst
operating
within
PIII/PV═O
redox
cycling
shown
capture
HNO,
generated
in
situ
by
Nef
decomposition
2-nitropropane,
selectively
install
amino
group
at
aryl
Csp2
centers.
The
method
furnishes
versatile
arylamines
from
acid
substrates
with
preservation
otherwise
reactive
functional
groups.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(18), P. 8242 - 8248
Published: May 2, 2022
An
organophosphorus-catalyzed
C–N
bond-forming
reductive
coupling
of
nitroalkanes
with
arylboronic
acids
and
esters
is
reported.
The
method
shows
excellent
chemoselectivity
for
the
nitro/boronic
acid
substrate
pair,
allowing
synthesis
N-(hetero)arylamines
rich
in
functionalization.
identification
a
sterically
reduced
phosphetane
catalyst
capable
productive
P(III)/P(V)═O
redox
manifold
key
enabling
development.
Combined
experimental
kinetics
computational
mechanistic
studies
show
that
affects
post-rate-limiting
steps
to
enable
event
preference
deleterious
side-paths.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(29), P. 16150 - 16159
Published: July 12, 2023
Palladium-catalyzed
C-N
bond
forming
reactions
are
a
key
tool
in
modern
synthetic
organic
chemistry.
Despite
advances
catalyst
design
enabling
the
use
of
variety
aryl
(pseudo)halides,
necessary
aniline
coupling
partner
is
often
synthesized
discrete
reduction
step
from
nitroarene.
An
ideal
sequence
would
avoid
necessity
this
while
maintaining
reliable
reactivity
palladium
catalysis.
Herein,
we
describe
how
reducing
conditions
enable
new
chemical
steps
and
well-studied
catalysts,
resulting
new,
useful
transformation:
reductive
arylation
nitroarenes
with
chloroarenes
to
form
diarylamines.
Mechanistic
experiments
suggest
that
under
conditions,
BrettPhos-palladium
complexes
catalyze
dual
Chemistry - An Asian Journal,
Journal Year:
2020,
Volume and Issue:
15(20), P. 3209 - 3224
Published: Aug. 14, 2020
In
2005,
a
facile
dihydrogen
activation
was
reported
by
the
Power
group
using
an
alkyne
analog
of
germanium
[ArGe≡GeAr;
Ar=2,6-Trip2
-C6
H3
(Trip=2,4,6-i
Pr3
H2
)].
After
that,
significant
progress
has
been
made
in
various
small
molecules
main-group
compounds,
and
variety
stoichiometric
catalytic
processes
have
formulated
p-block
elements.
this
regard,
compounds
containing
low-valent
elements
with
frontier
orbitals
relatively
energy
gaps
or
forming
frustrated
Lewis
pair
(FLP)
became
quite
successful.
spite
these
promising
transformations,
redox-cycling
catalysts
based
on
remain
extremely
rare.
Recently,
it
observed
that
pincer
type
ligands
supported
geometry
constrained
are
capable
acting
as
redox
similar
to
those
transition
metals.
review,
we
focus
synthesis
structural
aspects
ligands.
Emphasis
placed
their
applications
activity
activation.
