Organometallics,
Journal Year:
2023,
Volume and Issue:
42(12), P. 1291 - 1299
Published: March 8, 2023
The
mechanism
of
zirconium-catalyzed
hydroaminoalkylation
diphenylacetylene,
and
the
origin
contrasting
reactivity
with
N-benzylaniline
or
N-(trimethylsilyl)benzylamine
substrates,
have
been
investigated.
Isolated
intermediates
revealed
that
nature
C–H
activation
C–C
bond-forming
steps
in
alkyne
are
analogous
to
those
alkene
variant,
regardless
amine
substrate.
In
alkynes,
open
coordination
sphere
at
zirconium
center,
supported
by
bis(ureate)
ligand,
enables
neutral
protic
donors.
This
is
essential
for
promoting
catalytic
turnover
these
reactions.
Under
conditions,
dimethylamine
acts
as
a
proton
source
releasing
allylic
products
while
minimizing
formation
side
products.
Additionally,
we
identified
homoleptic
tetra(ureate)
complex
main
catalyst
decomposition
pathway
hydroaminoalkylation.
similar
structures
further
favored
when
employing
smaller
bis(urea)
proligands,
thus
explaining
poor
performance
some
ligands
catalysis.
However,
increasing
proligand
size
minimize
such
favors
isomerization
side-products
resulting
reduced
yields
desired
product.
study
provides
ligand
design
principles
guide
development
coordinatively
flexible
catalysts
achieve
systems
rely
upon
protonolysis
steps,
ACS Organic & Inorganic Au,
Journal Year:
2022,
Volume and Issue:
3(2), P. 74 - 91
Published: Dec. 30, 2022
Organometallic
catalysis
is
a
powerful
strategy
in
chemical
synthesis,
especially
with
the
cheap
and
low
toxic
metals
based
on
green
chemistry
principle.
Thus,
selection
of
metal
particularly
important
to
plan
relevant
applicable
processes.
The
group
VB
have
been
subject
exciting
significant
advances
both
organic
inorganic
synthesis.
In
this
Review,
we
summarized
some
reports
from
recent
decades,
which
are
about
development
utilized
various
types
reactions,
such
as
oxidation,
reduction,
alkylation,
dealkylation,
polymerization,
aromatization,
protein
practical
water
splitting.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(23), P. 4293 - 4302
Published: Nov. 1, 2023
Abstract
The
intermolecular
anti‐Markovnikov
hydroamination
of
vinylsilanes
was
achieved
utilizing
five
silyl‐substituted
ortho
‐terphenoxide
yttrium
complexes.
highest
activity
observed
for
the
most
sterically
encumbered
triphenylsilyl‐substituted
complex.
Excellent
and
complete
anti‐Markonikov
selectivity
were
obtained
a
variety
benzylic
aliphatic
primary
secondary
amines.
Interestingly,
reaction
with
2‐picolylamine
produced
hydroaminoalkylation
product
rather
than
product.
Reaction
dimethyldivinylsilane
resulted
in
range
1,4‐azasilinanes
via
sequential
hydroamination/
endo
cyclization
good
yields.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: July 6, 2023
The
precise
activation
of
C-H
bonds
will
eventually
provide
chemists
with
transformative
methods
to
access
complex
molecular
architectures.
Current
approaches
selective
relying
on
directing
groups
are
effective
for
the
generation
five-membered,
six-membered
and
even
larger
ring
metallacycles
but
show
narrow
applicability
generate
three-
four-membered
rings
bearing
high
strain.
Furthermore,
identification
distinct
small
intermediates
remains
unsolved.
Here,
we
developed
a
strategy
control
size
strained
in
rhodium-catalysed
aza-arenes
applied
this
discovery
tunably
incorporate
alkynes
into
their
azine
benzene
skeletons.
By
merging
rhodium
catalyst
bipyridine-type
ligand,
three-membered
metallacycle
was
obtained
catalytic
cycle,
while
utilizing
an
NHC
ligand
favours
metallacycle.
generality
method
demonstrated
range
aza-arenes,
such
as
quinoline,
benzo[f]quinolone,
phenanthridine,
4,7-phenanthroline,
1,7-phenanthroline
acridine.
Mechanistic
studies
revealed
origin
ligand-controlled
regiodivergence
metallacycles.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(36), P. 6571 - 6575
Published: Sept. 7, 2022
A
tricatalytic
telescoped
synthesis
toward
C3-methyl-N-aryl
indoline
and
indole
products
is
reported.
An
in
situ
generated
tantalum(V)
ureate
catalyst
used
for
the
hydroaminoalkylation
of
o-chlorostyrene
with
N-methylaniline
to
first
make
a
Csp3─Csp3
bond.
Subsequent
nickel-catalyzed
C-N
coupling
forms
N-aryl
indolines,
if
desired,
subsequent
oxidation
indoles
can
be
achieved
using
catalytic
[Cu(MeCN)4]BF4
tert-butylperoxy-2-ethylhexyl
carbonate
as
terminal
oxidant.
This
strategy
highlights
an
alternative
C-C
bond
disconnection
indoles,
which
enabled
by
atom-economic
reaction.
The
method
was
streamlined
three-step,
two-pot
approach
afford
up
73%
overall
isolated
yield
variously
substituted
indoles.
Organometallics,
Journal Year:
2023,
Volume and Issue:
42(12), P. 1291 - 1299
Published: March 8, 2023
The
mechanism
of
zirconium-catalyzed
hydroaminoalkylation
diphenylacetylene,
and
the
origin
contrasting
reactivity
with
N-benzylaniline
or
N-(trimethylsilyl)benzylamine
substrates,
have
been
investigated.
Isolated
intermediates
revealed
that
nature
C–H
activation
C–C
bond-forming
steps
in
alkyne
are
analogous
to
those
alkene
variant,
regardless
amine
substrate.
In
alkynes,
open
coordination
sphere
at
zirconium
center,
supported
by
bis(ureate)
ligand,
enables
neutral
protic
donors.
This
is
essential
for
promoting
catalytic
turnover
these
reactions.
Under
conditions,
dimethylamine
acts
as
a
proton
source
releasing
allylic
products
while
minimizing
formation
side
products.
Additionally,
we
identified
homoleptic
tetra(ureate)
complex
main
catalyst
decomposition
pathway
hydroaminoalkylation.
similar
structures
further
favored
when
employing
smaller
bis(urea)
proligands,
thus
explaining
poor
performance
some
ligands
catalysis.
However,
increasing
proligand
size
minimize
such
favors
isomerization
side-products
resulting
reduced
yields
desired
product.
study
provides
ligand
design
principles
guide
development
coordinatively
flexible
catalysts
achieve
systems
rely
upon
protonolysis
steps,
