Secondary
amines
as
a
directing
group
for
C-H
activation
have
limitations
they
are
prone
to
undergo
oxidation,
allylic
deamination,
and
β-hydride
elimination.
The
fundamental
challenge
observed
here
is
the
competition
between
desired
versus
vulnerable
β-C-H
bond
of
secondary
amine
when
substrate
ligand
affinity
not
strong
enough.
Herein,
potential
axially
chiral
NOBINAc
revealed
accelerate
enantioselective
PdII-catalyzed
process
ferrocenyl
amines.
Further,
interaction
cesium
cation
with
sulfonate
plays
an
impressive
role
in
mitigating
threat
elimination
via
enhanced
affinity.
This
approach
resulted
activation,
intermolecular
annulation,
alkenylation
allenes
activated
olefines,
leading
ferrocene
fused
tetrahydropyridines
alkenylated
up
70%
yields
99:1
er.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
366(4), P. 774 - 779
Published: Oct. 26, 2023
Abstract
Rh‐catalyzed
asymmetric
C(
sp
3
)−H
arylation
of
8‐benzylquinolines
with
arylboronic
acids
was
developed.
In
the
presence
5
mol%
BINOL‐derived
chiral
cyclopentadienyl
rhodium
complex,
benzylic
bond
reaction
proceeded
smoothly
to
afford
a
series
enantioenriched
triarylmethanes
in
moderate
good
yields
excellent
enantioselective
control
(24–89%
yields,
63–93%
ee).
The
method
displays
broad
substrate
scope
and
functional
group
tolerance
under
mild
conditions.
Green Synthesis and Catalysis,
Journal Year:
2024,
Volume and Issue:
unknown
Published: March 1, 2024
Herein,
we
report
an
intramolecular
6-endo-dig
cyclization
of
N-ferrocenyl
propiolamides
for
the
synthesis
planar
chiral
ferrocenes
enabled
by
gold(I)-catalyzed
hydroarylation.
By
using
this
protocol,
a
variety
ferrocenopyridin-2(1H)-ones
were
obtained
in
good
yields
and
excellent
enantioselectivities
(up
to
96%
ee).
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(12), P. 2387 - 2392
Published: March 15, 2024
[2.2]Paracyclophane-fused
heterocycles
represent
an
important
scaffold.
Traditional
approaches
often
suffer
from
tedious
synthetic
routes,
and
the
development
of
catalytic
synthesis
them
remains
in
its
infancy.
Herein,
by
employing
highly
strained
aryne
intermediates
as
partners,
we
have
developed
a
concise
protocol
palladium-catalyzed
C–H
activation/annulation
[2.2]paracyclophanecarboxamide
substrates.
quinolinone
products
are
obtained
good
yields
(up
to
84%).
Furthermore,
utility
process
has
been
shown
through
[2.2]paracyclophane-fused
heterocyclic
catalysts.
Secondary
amines
as
a
directing
group
for
C-H
activation
have
limitations
they
are
prone
to
undergo
oxidation,
allylic
deamination,
and
β-hydride
elimination.
The
fundamental
challenge
observed
here
is
the
competition
between
desired
versus
vulnerable
β-C-H
bond
of
secondary
amine
when
substrate
ligand
affinity
not
strong
enough.
Herein,
potential
axially
chiral
NOBINAc
revealed
on
accelerating
enantioselective
Pd(II)-catalyzed
process
ferrocenyl
amines.
Further,
interaction
cesium
cation
with
sulfonate
plays
an
impressive
role
in
mitigating
threat
elimination
via
enhanced
affinity.
This
approach
resulted
intermolecular
annulation
allenes,
leading
ferrocene
fused
tetrahydropyridines
up
70%
yields
98%
ee.
Secondary
amines
as
a
directing
group
for
C-H
activation
have
limitations
they
are
prone
to
undergo
oxidation,
allylic
deamination,
and
β-hydride
elimination.
The
fundamental
challenge
observed
here
is
the
competition
between
desired
versus
vulnerable
β-C-H
bond
of
secondary
amine
when
substrate
ligand
affinity
not
strong
enough.
Herein,
potential
axially
chiral
NOBINAc
revealed
accelerate
enantioselective
PdII-catalyzed
process
ferrocenyl
amines.
Further,
interaction
cesium
cation
with
sulfonate
plays
an
impressive
role
in
mitigating
threat
elimination
via
enhanced
affinity.
This
approach
resulted
activation,
intermolecular
annulation,
alkenylation
allenes
activated
olefines,
leading
ferrocene
fused
tetrahydropyridines
alkenylated
up
70%
yields
99:1
er.
