A
novel
pyridyl-thiadiazole
ligand
has
been
designed,
synthesized,
and
employed
in
the
preparation
of
a
heterogeneous
iridium
catalyst
supported
on
multi-hydroxyl
polyhedral
oligomeric
silsesquioxane.
The
as-prepared
exhibits
excellent
catalytic
activity
one-pot
cascade
selective
synthesis
N-/C-substituted
indole
derivatives
from
amino
alcohols
via
borrowing
hydrogen
strategy.
Meanwhile,
it
was
observed
that
this
approach
good
functional
group
tolerance
broad
substrate
scope.
Notably,
by
employing
system,
an
inhibitor
against
gp41-mediated
HIV-1
fusion
core
structure
could
be
conveniently
synthesized
2-aminophenethyl
alcohol
benzyl
40.6%
total
yield
for
only
four
steps
“borrowing
hydrogen”
Mechanistic
explorations
showed
transformation
undergoes
processes,
involving
N/C-alkylation
through
strategy,
oxidative
cyclization.
Recycling
experiments
disclosed
easily
recovered
reused
at
least
seven
times
with
TON.
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(6), С. 3989 - 4000
Опубликована: Март 8, 2022
Herein,
we
demonstrated
Mn-catalyzed
selective
C-3
functionalization
of
indoles
with
alcohols.
The
developed
catalyst
can
also
furnish
bis(indolyl)methanes
from
the
same
set
substrates
under
slightly
modified
reaction
conditions.
Mechanistic
studies
reveal
that
is
going
via
a
borrowing
hydrogen
pathway.
To
highlight
practical
utility,
diverse
range
including
nine
structurally
important
drug
molecules
are
synthesized.
Furthermore,
introduced
one-pot
cascade
strategy
for
synthesizing
functionalized
directly
2-aminophenyl
ethanol
and
alcohol.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(9), С. 5827 - 5843
Опубликована: Апрель 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
Advanced Synthesis & Catalysis,
Год журнала:
2021,
Номер
363(22), С. 5028 - 5046
Опубликована: Сен. 22, 2021
Abstract
C‐methylation
is
a
vitally
important
reaction
applicable
in
chemical
synthesis
and
structure‐based
drug
design.
Notably,
the
“magic
methyl”
effect
has
become
decisive
medicinal
chemistry
discovery
for
modulation
of
bio‐active
properties
life
science
molecules.
In
this
regard,
widely
applied
modification
various
biomolecules,
pharmaceuticals,
natural
products.
general,
often
relies
on
activated,
hazardous
uneconomical
methyl
sources
such
as
diazomethane,
dimethyl
sulfate,
halides.
To
achieve
methylation
reactions
sustainable
cost‐effective
manner,
use
‘ideal’
C1
source
crucial.
methanol
constitutes
an
expedient
−CH
3
because
simple
alcohol
less‐hazardous,
inexpensive,
abundantly
available
platform
well
it
produces
only
water
by‐product
processes.
Regarding
potential
catalysts
to
perform
using
by
hydrogen
borrowing
methodology,
non‐noble
metal‐based
are
highly
preferable
due
their
unique
advantages
more
abundance,
inexpensive
low‐toxicity.
recent
years,
chemists
made
significant
contributions
towards
catalytic
valorization
insert
groups
via
C−H
activation
variety
compounds
Consequently,
minireview
we
summarize
process
applying
Fe‐,
Mn‐,
Co‐
Ni‐based
metal
free
catalysts.
magnified
image
ACS Catalysis,
Год журнала:
2024,
Номер
14(3), С. 1629 - 1638
Опубликована: Янв. 17, 2024
Recent
findings
show
pincer
catalysts
of
osmium
superior
in
a
broad
spectrum
synthetically
valuable
transformations.
This
article
reports
structurally
well-defined
Os(II)PCsp3P
complexes
stabilized
by
functional
dibenzobarrelene-based
ligand.
We
describe
their
organometallic
and
catalytic
properties
the
hydride
transfer
reactions.
demonstrate
that
center,
covalently
locked
within
3-dimensional
ligand
pocket,
exhibits
strictly
predictable
coordination
behavior
redox
rigidity
while
remaining
catalytically
active
owing
to
potential
cooperation
with
proximate
side
arm.
The
described
were
found
as
mild
selective
methylation
alcohols,
indoles,
phenols,
sulfonamides
using
methanol
C1
source.
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(9), С. 5603 - 5616
Опубликована: Апрель 13, 2022
We
disclosed
a
regio-selective
C–H
and
N–H
bond
functionalization
of
indolines
using
alcohols
in
water
via
tandem
dehydrogenation
N-heterocycles
alcohols.
A
diverse
range
N-
C3-alkylated
indolines/indoles
were
accessed
utilizing
new
cooperative
iridium
catalyst.
The
practical
applicability
this
methodology
was
demonstrated
by
the
preparative-scale
synthesis
psychoactive
drug,
N,N-dimethyltryptamine.
catalytic
cycle
is
proposed
based
on
several
kinetic
experiments,
series
control
experiments
density
functional
theory
calculations.
Chemistry - An Asian Journal,
Год журнала:
2022,
Номер
17(17)
Опубликована: Июнь 30, 2022
The
catalytic
dehydrogenation
of
alcohols
is
essential
for
the
sustainable
production
valuable
products.
This
provides
a
new
strategy
green
organic
synthesis
in
chemical
industries.
Herein,
we
describe
manganese-based
system
that
enables
efficient
C3-alkylated
indoles
from
benzyl
and
via
borrowing
hydrogen
process.
Furthermore,
dehydrogenative
coupling
2-arylethanols
yields
C3-alkenylated
indoles.
Meanwhile,
reacting
2-aminophenethanol
instead
can
also
obtain
corresponding
indole
products
with
high
selectivity
under
same
conditions.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 29, 2025
We
have
developed
efficacious
routes
toward
the
selective
synthesis
of
two
classes
compounds
such
as
C-3
amino-methylated
indoles
and
4-indol-3-yl-methylanilines
from
same
precursors,
namely,
1,3,5-triazinanes.
It
is
reported
that
controlled
cleavage
1,3,5-triazinanes
can
be
effected
by
heat
for
generation
aryl
imine
motifs,
we
observed
presence
Lewis
acid
influences
course
these
transformations
different
products.
The
reaction
indol-3-yl-methylanilines
proceeds
via
a
nucleophilic
attack
indole
to
generated
form
an
product
which
undergoes
mediated
Hofmann-Martius-type
rearrangement.
In
absence
acid,
between
1,3,5-triazinane
afforded
indoles.
Experimentally,
could
prove
was
intermediate
formed
during
catalyzed
process
in
intermolecular
fashion.
both
found
general,
library
molecules
generated.
