Acta Scientific Pharmaceutical Sciences,
Год журнала:
2023,
Номер
unknown, С. 37 - 47
Опубликована: Июнь 1, 2023
The
mechanism
is
investigated
for
Pd-catalyzed
carbo-aminative
cyclization
of
1,6-enyne
with
2-iodoaniline.The
regioselective
addition
Pd-inserted
2-iodoaniline
across
alkyne
and
intermolecular
insertion
olefin
leads
to
alkyne-to-alkene
adducts.After
isomerization,
a
pallado
intermediate
obtained
upon
aza-conjugate
addition.The
β-hydride
eliminated
the
help
Pd.The
oxidative
aromatization
promoted
by
carbonate
ion
makes
oxidation
level
consistent
desired
product.The
regioselectivity
6-endo-trig
determined
through
superiority
over
other
two
modes
in
Heck-type
intramolecular
coupling.The
promotion
active
Pd(0)
lies
barrier
decrease
rate-limiting
isomerization
especially
elimination.These
results
are
supported
Multiwfn
analysis
on
FMO
specific
TSs
MBO
value
vital
bonding,
breaking.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 2, 2025
Complementary
methods
toward
the
selective
functionalization
of
indole
and
oxindole
frameworks
employing
an
alternative
strategy
in
heteroaryl
C–H
functionalizations
are
presented
herein.
This
work
focuses
on
a
catalyst-controlled,
site
activation/functionalization
3-acyl
indoles,
wherein
amide
serves
as
robust
versatile
directing
group
capable
undergoing
concomitant
1,2-acyl
translocation/C–H
presence
RhI/AgI
co-catalysts
to
provide
cross-coupled
adducts
high
yields.
In
contrast,
use
IrIII/AgI
catalysts
subverted
migration
afford
corresponding
C2-functionalized
products
good
excellent
A
notable
feature
catalyst
systems
was
exceptional
level
selectivity
observed
which
functionalized
indoles
were
obtained
exclusively.
Mechanistic
experiments
indicate
concerted
step
metallation
occurring
through
electrophilic
aromatic
substitution
process.
Here,
authors
present
divergent,
transition
metal
catalyst-controlled
3-carboxamide
indoles.
One
set
conditions
enables
2-position,
while
other
translocation
carboxamide
at
3-position.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(24), С. 6063 - 6069
Опубликована: Янв. 1, 2023
A
simple,
mild,
and
metal-
extra-auxiliary
group-free
method
for
the
direct
arylation
of
indole-3-carbaldehydes
induced
by
an
in
situ
generated
transient
directing
group
was
developed.
Abstract
The
indole
scaffold
is
a
recurring
structure
in
multiple
bioactive
heterocycles
and
natural
products.
Substituted
indoles
like
the
amino
acid
tryptophan
serve
as
precursor
for
wide
range
of
products
with
pharmaceutical
or
agrochemical
applications.
Inspired
by
versatility
these
compounds,
medicinal
chemists
have
decades
exploited
core
drug
discovery
process.
With
aim
tuning
properties
lead
candidates,
regioselective
halogenation
common
strategy.
However,
chemical
generally
expensive,
has
poor
atom
economy,
lacks
regioselectivity,
generates
hazardous
waste
streams.
As
an
alternative,
this
work
we
engineer
industrial
workhorse
Saccharomyces
cerevisiae
de
novo
production
halogenated
tryptamine
derivatives.
Functional
expression
bacterial
halogenases
together
partner
flavin
reductase
decarboxylase
resulted
chlorine
bromine.
Furthermore,
combining
halogenases,
di‐halogenated
molecules
was
also
achieved.
Overall,
works
paves
road
new‐to‐nature
yeast.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 8, 2025
Direct
functionalization
of
native
(N–H)
indoles
via
C–H
activation
remains
a
challenge.
Herein,
we
report
salicylaldehyde-promoted
cobalt-catalyzed
selective
C2–H
Heck
reaction
with
both
active
and
unactivated
olefins
in
the
presence
free
N–H
bonds.
A
series
structurally
diverse
C2-alkenylated
including
natural
product
drug
derivatives
were
prepared
directly
effectively
without
additional
preprotection
deprotection
procedures.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 14, 2025
Tetrahydro-γ-carbolines
are
especially
outstanding
fused
heterocyclic
ring
systems
possessing
significant
biological
activities
in
the
central
nervous
system.
Here,
using
commercially
available
NBE
derivatives
(NBEs),
we
report
an
efficient
protocol
for
one-pot
modular
synthesis
of
4-substituted
tetrahydro-γ-carbolines
via
Catellani/aza-Michael
addition
cascade
from
easily
3-iodo-1-tosyl-1H-indole,
aziridines
and
olefins.
This
approach
exhibits
a
wide
substrate
scope,
good
yields,
scalability,
potential
extension
toward
Mebhydroline
analogues.
ACS Omega,
Год журнала:
2025,
Номер
10(20), С. 20497 - 20508
Опубликована: Май 14, 2025
This
study
presents
a
practical,
efficient,
and
scalable
approach
for
the
C-H
formylation
of
indoles
their
derivatives
using
alkyl
orthoesters
as
formylating
agents.
Boron
trifluoride
diethyl
etherate
(BF3·OEt2)
was
found
to
be
an
effective
stoichiometric
catalyst,
with
trimethyl
orthoformate
(TMOF)
acting
reliable
formyl
source.
method
enables
rapid
efficient
synthesis
wide
range
C-formylindoles,
including
C3,
C2,
C6,
C7
derivatives,
well
electron-rich
aromatic
carbaldehydes.
Key
advantages
protocol
include
its
operational
simplicity,
use
inexpensive
readily
available
reagents,
neat
conditions,
ambient
reaction
temperatures,
short
times
(typically
1-5
min),
broad
substrate
tolerance,
scalability.
These
features
make
highly
versatile
suitable
diverse
synthetic
applications.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(20), С. 14423 - 14434
Опубликована: Окт. 5, 2023
Regioselective
C–H
functionalizations
of
indoles
reported
to
date
with
directing
groups
at
C3
mainly
rely
on
functional
that
are
linked
the
indole
via
C–C
bonds.
However,
core
by
C–X
linkages
also
attractive
due
possibility
further
modifications
bond.
Herein,
we
report
a
3-acetoxy
group
for
regioselective
C2
alkenylation
activation-based,
cross-dehydrogenative,
oxidative
Heck-type
reaction.
The
reaction
is
catalyzed
Pd(II)
and
Ag(I)
stoichiometric
Cu(II)
as
oxidant
provides
2-alkenylated
in
yields
52–84%.
conditions
compatible
several
different
positions
well
N-protecting
or
free
NH
core.
With
respect
alkene
coupling
partners,
reactions
successful
acrylates,
vinyl
sulfates,
phosphates.
Specifically
designed
experiments,
density
theory
(DFT)
computational
studies,
reveal
heterodinuclear
[Pd(μ-OAc)3Ag]
bimetallic
species
actual
catalyst
responsible
alkenylation.
A
mechanistic
path
involving
this
catalytic
was
found
be
favorable
over
other
possible
pathways
explaining
observed
regioselectivity
through
DFT
studies.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(35), С. 7121 - 7127
Опубликована: Янв. 1, 2024
We
introduced,
for
the
first
time,
N
-methoxyamide
directed
proximal
C–H
bond
activation
of
imidazo[1,2-
a
]pyridines
C(sp
2
)–C(sp
)
formation
via
transition
metal
catalysed
approach
to
obtain
C-5
arylated
]pyridines.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 25, 2024
A
straightforward
preparation
of
diversified
fluorinated
indol-3-yl
ketones
was
developed
by
the
direct
decarboxylative
fluoroacylation
indole
carboxylic
acids.
The
reaction
could
be
performed
on
a
gram
scale
under
net
conditions.
Neither
metal
catalyst
nor
an
additive
employed.
This
methodology
featured
simple
conditions,
high
efficiency,
exclusive
selectivity,
broad
substrate
scope,
and
easy
operation,
which
allowed
it
to
meet
green
chemistry
requirement
modern
pharmaceutical
industry.
Control
experiments
confirmed
that
radical
process
might
involved
in
tandem
sequence.