ChemCatChem,
Journal Year:
2023,
Volume and Issue:
16(3)
Published: Nov. 27, 2023
Abstract
Palladium
nanohybrids
were
synthesized
and
applied
to
the
one‐pot
synthesis
of
bis(3‐indolyl)methanes
by
selective
C−C
bond
reaction
from
benzyl
alcohol
indole.
A
T.
lanuginosus
lipase‐palladium
nanoparticles
hybrid
(Pd@TLL)
was
synthesized,
yielding
PdNPs
with
an
average
diameter
size
5
nm.
This
heterogeneous
catalyst
first
tested
in
oxidation
benzaldehyde
different
solvents.
Then,
direct
formation
bis(3‐indolyl)methane,
situ
coupling,
successfully
evaluated
under
conditions,
obtaining
>99
%
conversion
at
80
°C
toluene,
a
TOF
value
9
min
−1
89
pure
water
,
demonstrating
versatility
these
biohybrids.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(9), P. 4607 - 4647
Published: Jan. 1, 2024
This
review
collectively
discussed
the
utilisation
of
alcohols
in
various
organic
transformations
and
their
application
toward
intermediates
drugs,
drug
derivatives
natural
product-like
molecules.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(9), P. 5827 - 5843
Published: April 10, 2023
Herein,
we
report
azo-benzimidazole
containing
cobalt
complexes
(1-3)
for
alcohol
dehydrogenation-triggered
C3-alkylation
of
indoles.
In
1-3,
ligands
are
redox
noninnocent
and
showed
facile
irreversible
L/L•
reduction
followed
by
Co(II)/Co(I)
in
close-lying
potentials.
Taking
advantage
events
the
first
aerial
dehydrogenation
alcohols
to
their
corresponding
carbonyl
compounds
is
explored.
Subsequently,
indole
was
studied
using
as
alkylating
agents.
The
developed
catalytic
protocol
found
be
efficient
very
selective.
It
has
a
broad
substrate
scope
good
functional
group
tolerance.
As
far
aware,
it
homogeneous
catalyst
agent.
Detailed
mechanistic
studies,
including
deuterium
labeling
experiment,
have
suggested
borrowing
hydrogen
method
indole.
coordinated
ligand,
cooperatively
with
couple,
oxidized
alkoxide
radical
pathway
result
compound
(Scheme
1),
which
on
subsequent
condensation
generates
alkylideneindolenine
intermediate
"X".
Reduction
"X"
an
azo-anion
Co(I)
resulted
C3-alkylated
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(9), P. 5944 - 5961
Published: April 13, 2023
A
Ru(II)-catalyzed
efficient
and
selective
N-alkylation
of
amines
by
C1-C10
aliphatic
alcohols
is
reported.
The
catalyst
[Ru(L1a)(PPh3)Cl2]
(1a)
bearing
a
tridentate
redox-active
azo-aromatic
pincer,
2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline
(L1a)
air-stable,
easy
to
prepare,
showed
wide
functional
group
tolerance
requiring
only
1.0
mol
%
(for
N-methylation
N-ethylation)
0.1
loading
for
with
C3-C10
alcohols.
array
N-methylated,
N-ethylated,
N-alkylated
were
prepared
in
moderate
good
yields
via
direct
coupling
1a
efficiently
catalyzes
the
diamines
selectively.
It
even
suitable
synthesizing
using
(aliphatic)
diols
producing
tumor-active
drug
molecule
MSX-122
yield.
excellent
chemo-selectivity
during
oleyl
alcohol
monoterpenoid
β-citronellol.
Control
experiments
mechanistic
investigations
revealed
that
1a-catalyzed
reactions
proceed
borrowing
hydrogen
transfer
pathway
where
removed
from
dehydrogenation
step
stored
ligand
backbone
1a,
which
subsequent
steps
transferred
situ
formed
imine
intermediate
produce
amines.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(10)
Published: Feb. 7, 2024
Abstract
Herein
we
report
a
sustainable
approach
for
the
alkylation
of
ketones,
9
H
‐fluorene,
oxindole,
and
indole
using
alcohols
as
alkylating
agent
catalyzed
by
well‐defined
air‐stable
zinc
catalyst
(
1
)
tridentate
redox
non‐innocent
arylazo
ligand,
2‐((4‐chlorophenyl)diazenyl)‐1,10‐phenanthroline
L
).
2–3
mol
%
efficiently
produces
substituted
α‐alkylated
9‐alkylated
fluorenes,
C3
‐alkylated
oxindoles,
indoles
in
moderate
to
good
isolated
yields.
In
aerial
condition,
formation
bis(indolyl)methane
(BIMs)
derivatives
were
observed
when
subjected
primary
alcohols.
A
few
drug
molecules
containing
BIMs
prepared
The
exhibited
chemoselectivity
during
functionalization
fluorene
with
oleyl
alcohol
β‐citronellol.
control
experiments,
including
deuterium
labeling
performed
unveil
reaction
mechanism
indicate
that
one‐electron
reduced
azo‐anion
radical
species
[
]‐formed
situ,
acts
active
catalyst.
All
events
occur
at
redox‐active
aryl‐azo
which
reservoir
hydrogen
electrons
throughout
catalytic
cycle,
keeping
Zn(II)‐center
template.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(17), P. 3502 - 3509
Published: Jan. 1, 2024
An
expeditious
metal
free
C-3
alkylation
of
indoles
and
its
NIS-mediated
deviation
to
indolo[2,3-
b
]quinolines
is
reported.
Applications
these
strategies
in
accessing
bioactive
natural
products
have
also
been
demonstrated.
Catalysis Science & Technology,
Journal Year:
2023,
Volume and Issue:
13(11), P. 3358 - 3365
Published: Jan. 1, 2023
New
orthometallated
Pd(
ii
)
C^N^S
pincer
catalyst-mediated
sustainable
and
cost-effective
synthesis
of
pharmacologically
important
bis(indolyl)methanes
(23
examples
up
to
95%
yield)
via
ADC
is
reported.
ChemistryOpen,
Journal Year:
2023,
Volume and Issue:
12(1)
Published: Jan. 1, 2023
The
indole
moiety
is
an
important
N-heterocycle
found
in
natural
products,
and
a
key
structural
component
of
many
value-added
chemicals
including
pharmaceuticals.
In
particular,
bis(3-indolyl)methanes
(BIMs)
are
subgroup
indoles,
composed
two
units.
Herein,
we
report
the
development
simple
method
to
access
BIMs
derivatives
yields
up
77
%
by
exploiting
tBuOK-mediated
coupling
reaction
indoles
benzyl
alcohols.
