Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
363(16), P. 3868 - 3878
Published: April 30, 2021
Abstract
Directing
group‐assisted
C−H
activation
has
been
widely
used
to
control
regioselectivity
in
the
field
of
transition‐metal‐catalyzed
functionalization.
Common
functionalities
found
complex
organic
molecules
and/or
readily
available
reagents
are
most
appealing
directing
groups,
as
they
circumvent
need
install/remove
group.
The
aldehyde
group
is
an
important
functional
many
areas
including
pharmaceuticals
and
material
science.
In
this
review,
we
present
current
state‐of‐the‐art
aldehyde‐assisted,
sp
2
functionalization
arenes.
magnified
image
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(18), P. 8079 - 8091
Published: April 25, 2024
Density
functional
theory
(DFT)
calculations
have
been
conducted
to
elucidate
the
detailed
mechanisms
of
yttrium-catalyzed
C–H
polyaddition
1,4-dimethoxybenzene
(DMB)
1,4-divinylbenzene
(DVB).
It
was
computationally
determined
that
DMB
not
only
serves
as
a
substrate
but
also
performs
crucial
role
ligand,
stabilizing
catalytically
active
species
and
promoting
alkene
insertion.
Side
pathways
involving
Cβ–H
activation
C═C
continuous
insertion
were
excluded
due
steric
electronic
factors,
respectively,
explaining
why
reaction
occurred
efficiently
selectively
give
perfectly
alternating
DMB–DVB
polymers.
Interestingly,
theoretical
prediction
reactivity
N,N-dimethyl-1,4-phenylenediamine
2,2′-biethyl-4,4′-bipyridine
reveals
significant
differences
in
coordination
effects
these
substrates,
leading
distinct
mechanisms,
primarily
influenced
by
their
effects.
These
findings
shed
new
light
on
previously
overlooked
ligand
rare-earth-catalyzed
step-growth
copolymerization
reactions.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
Herein,
we
report
a
method
for
the
regioselective
alkylation
and
phosphonation
of
quinoline
C4–H
via
B3H7-mediated
nucleophilic
addition
Turbo
Grignard
reagents
phosphine
oxide
anions
to
quinolines
bearing
different
substituents,
affording
4-alkyl
4-phosphoryl
tetrahydroquinolines
after
one-pot
oxidation
or
reduction.
The
results
indicate
that
coordination
B3H7
group
can
activate
substrates
toward
potential
1,4-dearomative
subtly
control
regioselectivity
by
preventing
1,2-dearomative
addition.
Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 11, 2025
The
rare-earth-catalyzed
C-H
alkylation
of
heteroatom-containing
substrates
with
alkenes
has
been
extensively
studied
over
the
past
decade.
Traditionally,
those
have
regarded
primarily
as
reactants
in
these
reactions.
In
this
study,
mechanism
2-ethylpyridine
styrene
was
investigated
by
DFT
calculations,
revealing
often-overlooked
ligand
effect
pyridine
substrates.
Our
findings
demonstrate
that
substrates,
acting
ligands,
play
a
pivotal
role
modulating
site
selectivity
during
activation.
These
results
enhance
our
understanding
rare-earth
catalysis
and
provide
valuable
insights
into
its
versatile
reactivity,
offering
novel
perspective
on
dual
roles
(both
reactant
ligand)
which
are
widely
used
functionalization
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
61(7)
Published: Dec. 15, 2021
Here
we
report
for
the
first
time
regio-
and
diastereoselective
[3+2]
annulation
of
a
wide
range
aliphatic
aldimines
with
alkenes
via
activation
an
unactivated
β-C(sp3
)-H
bond
by
half-sandwich
scandium
catalysts.
This
protocol
offers
straightforward
atom-efficient
route
synthesis
new
family
multi-substituted
aminocyclopentane
derivatives
from
easily
accessible
alkenes.
The
styrenes
exclusively
afforded
5-aryl-trans-substituted
1-aminocyclopentane
excellent
diastereoselectivity
through
2,1-insertion
styrene
unit.
selectively
gave
4-alkyl-trans-substituted
products
in
1,2-insertion
fashion.
A
catalytic
amount
appropriate
amine
such
as
adamantylamine
(AdNH2
)
or
dibenzylamine
(Bn2
NH)
showed
significant
effects
on
catalyst
activity
stereoselectivity.
Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
363(16), P. 3868 - 3878
Published: April 30, 2021
Abstract
Directing
group‐assisted
C−H
activation
has
been
widely
used
to
control
regioselectivity
in
the
field
of
transition‐metal‐catalyzed
functionalization.
Common
functionalities
found
complex
organic
molecules
and/or
readily
available
reagents
are
most
appealing
directing
groups,
as
they
circumvent
need
install/remove
group.
The
aldehyde
group
is
an
important
functional
many
areas
including
pharmaceuticals
and
material
science.
In
this
review,
we
present
current
state‐of‐the‐art
aldehyde‐assisted,
sp
2
functionalization
arenes.
magnified
image
