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.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(7), С. 1531 - 1537
Опубликована: Янв. 31, 2024
Abstract
Mn(II)‐catalyzed
alkylations
of
methyl
N
‐heteroarenes
was
reported
via
borrowing
hydrogen
strategy
with
alcohols
as
the
alkylating
reagent.
The
developed
geometry‐constrained
benzimidazole‐iminopyridyl
ligand
played
a
key
role
in
promoting
transformation
and
stablizing
metal
center.
A
wide
range
(aromatic,
heteroaromatic
aliphatic)
‐Heteroarenes
could
be
able
to
apply
current
catalytic
system,
TON
up
7400.
Organic Letters,
Год журнала:
2022,
Номер
24(49), С. 9054 - 9059
Опубликована: Дек. 5, 2022
A
one-pot
cascade
approach
for
the
synthesis
of
N-substituted
indoles
from
amino
alcohols
and
under
additive
base-free
conditions
with
liberation
water
as
only
stoichiometric
byproduct
is
reported.
The
commercially
available
bench-stable
Ni(OTf)2
salt
in
combination
1,2-bis(dicyclohexylphosphino)ethane
(dcype)
very
effective
this
unprecedented
catalytic
transformation.
broad
range
substrates
including
aromatic
aliphatic
primary
alcohols,
cyclic
acyclic
secondary
various
substituted
2-aminophenyl
ethyl
are
employed
reaction
to
provide
a
diverse
N-alkylated
indoles.
Mechanistic
studies
revealed
that
proceeds
through
tandem
N-alkylation
via
hydrogen
autotransfer
followed
by
cyclization
alcohol
intermediate.
Abstract
Herein,
we
present
an
efficient,
one‐pot
reaction
for
accessing
3‐benzylated
indoles
via
the
coupling
of
benzyl
alcohols
with
under
heterogeneous
catalysis
by
manganese
ferrite
(MnFe
2
O
4
)
nanoparticles.
Notably,
this
reaction,
first
time,
employs
MnFe
nanoparticles
prepared
using
a
simple
grinding
method.
The
high
compatibility
enables
broad
substrate
scope
and
regioselectivity.
Moreover,
approach
offers
several
attractive
highlights
including
use
recyclable
oxide
catalyst
green
cost‐effective
alkylating
reagents
solvent‐free
conditions.
Catalysis Science & Technology,
Год журнала:
2023,
Номер
13(19), С. 5745 - 5756
Опубликована: Янв. 1, 2023
We
report
manganese-catalyzed
CH
alkylation
of
indole/indolines
with
alcohols,
where
catalyst
control
provides
product
selectivity.
synthesise
several
life
science
molecules
(vibrindole
A,
turbomycin
B
alkaloid
and
antileukemic
anticancer
agents).
Organometallics,
Год журнала:
2022,
Номер
42(1), С. 38 - 47
Опубликована: Дек. 23, 2022
Reported
herein
is
a
well-defined
geometry-constrained
tridentate
N,N,O-nickel
complex
for
selective
α-alkylation
of
unactivated
amides
using
readily
available
alcohols
as
the
alkylating
reagents.
The
newly
developed
transformation
could
accommodate
broad
substrate
scope
including
various
substituted
benzylic
or
aliphatic
and
tertiary/secondary
acyclic
lactams.
tolerance
methanol
ethanol
in
this
protocol
provided
novel
possibility
carbon
chain
homologation
amides.
Mechanistic
studies
suggested
that
reaction
proceeds
through
borrowing
hydrogen
pathway.
Synthesis,
Год журнала:
2022,
Номер
55(09), С. 1460 - 1466
Опубликована: Дек. 22, 2022
Abstract
By
employing
either
borrowing
hydrogen
or
transfer
hydrogenation
strategy,
two
straightforward
[Ru(p-cymene)Cl2]2-catalyzed
methods
for
regioselective
synthesis
of
C3-alkylated
indoles
have
been
developed,
utilizing
alcohols
as
H
atom
donors
alkylating
agents.
The
developed
catalytic
system
could
accommodate
a
broad
substrate
scope
including
primary/secondary
aliphatic
and
substituted
indoles,
in
most
cases
providing
good
yields.
Notable
features
the
include
high-activity,
easy
operation,
air
atmosphere.
Organic Letters,
Год журнала:
2023,
Номер
25(39), С. 7100 - 7104
Опубликована: Сен. 28, 2023
C-H
methylation
of
heteroarenes
(e.g.,
indoles,
pyrroles,
etc.)
is
frequently
applied
in
the
synthesis
drug/biorelated
compounds.
We
herein
report
use
CO
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(43), С. 8651 - 8657
Опубликована: Янв. 1, 2023
The
transition
metal-free
Cs2CO3/Oxone®-mediated
C3-alkylation
of
indoles
proceeds
in
moderate
to
high
yields
with
a
variety
C4-C7
functionalized
and
is
applicable
2-,
3-
4-hydroxymethyl
pyridines
related
electron-deficient
heterocycles,
permitting
novel
late-stage
drug
functionalizations.
Preliminary
mechanistic
studies
support
hydrogen
autotransfer-type
chain
process
starting
an
initial
oxidation
the
alcohol
corresponding
aldehyde,
followed
by
subsequent
condensation
onto
indole
reduction/hydride
delivery
from
another
equivalent
primary
alcohol.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(9), С. 6000 - 6015
Опубликована: Апрель 15, 2024
Developing
a
highly
efficient
atom-economic
method
for
the
preparation
of
3-(1-heteroarylethyl)-indole
scaffolds
is
significant
value
in
pharmaceutical
and
agricultural
chemistry.
Herein,
phosphoric
acid-catalyzed
N-addition
reaction
3-vinyl
indoles
with
pyrazoles
C-addition
pyrazolones
were
developed.
A
series
pyrazole-substituted
synthesized
excellent
yields
(up
to
99%
yield)
under
mild
conditions.
reasonable
mechanism
was
proposed
explain
experimental
results.
Synlett,
Год журнала:
2024,
Номер
35(20), С. 2508 - 2514
Опубликована: Авг. 12, 2024
Abstract
Herein,
we
report
a
straightforward
approach
for
synthesizing
C3-alkylated
indoles
selectively
via
an
iron-catalyzed
alkylation
of
using
alcohols
as
the
alkylating
agents.
A
well-defined,
air-stable,
and
easy-to-prepare
Fe(II)
catalyst
redox-active
tridentate
arylazo
scaffold
was
used
catalyst.
Various
were
prepared
in
moderate
to
good
isolated
yields
by
coupling
with
different
substituted
alcohols.
The
methodology
is
compatible
gram-scale
synthesis.
Control
experiments
performed
unveil
mechanism,
which
revealed
that
reaction
proceeds
borrowing-hydrogen
pathway
where
coordinated
azo-aromatic
ligand
actively
participates
during
catalysis,
acting
electron
hydrogen
reservoir.
