Advancement in the C–H bond alkylation of (hetero)arenes catalyzed by the most abundant transition metal–iron
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(8), С. 2397 - 2417
Опубликована: Янв. 1, 2024
Advancement
in
the
direct
C–H
bond
alkylation
of
arenes
and
heteroarenes
using
catalysts
based
on
most
abundant
transition
metal,
iron,
is
summarized.
Язык: Английский
Three-Coordinate Iron(0) Complex-Catalyzed Regioselective C–H Alkylation of Indole Derivatives
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 17, 2025
The
synthesis
of
alkylated
indoles,
which
are
key
intermediates
for
various
drugs
and
bioactive
molecules,
is
great
importance.
However,
most
reports
on
the
functionalized
indoles
use
toxic
expensive
4d
or
5d
metal
catalysts,
limiting
further
application
these
methods.
Herein,
we
disclose
a
versatile
regioselective
C–H
alkylation
indole
derivatives
using
well-defined
three-coordinate
iron(0)
complex.
Neither
Grignard
reagents
nor
additional
additives
required,
making
reaction
sustainable,
environmentally
friendly,
compatible
with
broad
variety
functional
groups
to
afford
C2-alkylated
in
high
yields.
In
addition,
by
variation
aryl
substituent
alkene
substrate
trisubstituted
silyl
group,
regioselectivity
can
be
altered
from
Markovnikov
anti-Markovnikov.
Detailed
mechanistic
studies
revealed
catalytic
mode
reaction.
Язык: Английский
Divergent Synthesis of Di‐ and Mono‐Alkylated Indoles via Tunable Iron‐Catalyzed Hydroarylation of Styrenes
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(10), С. 2226 - 2233
Опубликована: Март 23, 2024
Abstract
We
report
an
iron‐catalyzed
divergent
synthesis
of
alkylated
indoles
based
on
precise
control
the
activation
sites
through
selection
catalysts.
Using
and
styrenes
as
starting
materials,
3,5‐
di
‐alkylated
could
be
prepared
selectively
directly
for
first
time
by
treating
with
a
catalytic
amount
Fe(OTf)
3
3‐alkylated
were
achieved
exclusively
adding
γ
‐cyclodextrin
cocatalyst
.
This
simple
method
was
demonstrated
52
examples
high
yields
broad
functional
group
compatibilities.
Язык: Английский
Iron-catalyzed Selective Construction of Indole Derivatives via Oxidative C(sp3)-H Functionalization of Indolin-2-ones
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(15), С. 3073 - 3079
Опубликована: Янв. 1, 2024
We
have
developed
a
clean
and
efficient
iron-catalyzed
C(sp
3
)–H
functionalization
of
indolin-2-ones
for
the
chemodivergent
synthesis
value-added
indole
derivatives,
including
isatins,
symmetrical
non-symmetrical
isoindigos.
Язык: Английский
Nickel‐Catalyzed Branch‐Selective C−H Alkylation of Indoles and Azoles with Alkenes: An Additive‐ and Solvent‐Free Approach
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(26)
Опубликована: Апрель 10, 2024
Abstract
The
development
of
sustainable
protocols
for
the
synthesis
alkylated
heteroarenes
is
crucial
owing
to
their
widespread
existence
in
medicinally
relevant
and
bioactive
natural
products.
Herein,
we
describe
an
efficient,
additive‐
solvent‐free
approach
regioselective
C−H
alkylation
indoles
azoles
with
alkenes
using
a
nickel
catalyst,
which
proceeds
through
chelation‐assistance
strategy.
reaction
exclusively
provided
branched
products
compatibility
alkyl,
alkoxy,
fluoro,
trifluoromethyl,
alkene,
cyano,
ester,
carbonyl
groups.
This
protocol
applicable
other
heteroarenes,
such
as
imidazoles
benzimidazoles,
providing
desired
exclusive
Markovnikov
selectivity.
synthetic
utility
scale‐up
are
demonstrated,
concord
principles
green
chemistry.
Alkylation
facile
reversible
nickelation
alkene
insertion
processes,
presumably
involving
rate‐limiting
reductive
elimination.
Язык: Английский
Iron-Catalyzed Functionalization of Heterocycles Through C─H Activation
Topics in heterocyclic chemistry,
Год журнала:
2024,
Номер
unknown, С. 1 - 32
Опубликована: Янв. 1, 2024
Язык: Английский
Palladium‐Catalyzed Regioselective C(4)−H Fluoroalkoxylation of Indoles through Weak Chelation Assistance
ChemCatChem,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 10, 2024
Abstract
Installing
fluoroalkyl
motifs
into
biorelevant
indoles
is
particularly
interesting
due
to
their
ubiquitous
presence
in
drug
molecules.
Herein,
we
demonstrate
the
regioselective
C4
fluoroalkoxylation
of
using
fluoroalcohols
via
palladium‐catalyzed
chelation‐assisted
C─H
activation.
The
weak
chelating
benzoyl
moiety
at
C3
position
acts
as
a
directing
group
for
remote
C(4)─H
diversely
substituted
indoles.
This
methodology
demonstrates
high
level
regioselectivity
and
tolerates
range
crucial
functional
groups,
yielding
diverse
trifluoroalkoxylated
moderate
good
yields.
Removal
directing/protecting
groups
further
functionalization
established
synthetic
utility
methodology.
A
preliminary
mechanistic
investigation
conducted
by
isolating
palladacycle
intermediate
performing
deuterium
scrambling
study.
Язык: Английский
Base‐Promoted Structural Rearrangement of Ynamide and Simultaneous N‐Desulfonylation
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(7), С. 1615 - 1626
Опубликована: Фев. 7, 2024
Abstract
Herein,
we
describe
a
base‐promoted
regioselective
and
chemoselective
cascade
cyclization,
ynamide
N−C
sp
bond
cleavage,
selective
intramolecular
1,3‐migration,
simultaneous
N
‐desulfonylation
strategy
for
the
synthesis
of
2‐phenyl‐3‐(phenylethynyl)‐1H‐indole
derivatives.
We
observed
multiple
breaking
(−N−Ts,
C
2
−Ts,
−I/C
−SePh)
from
(
E
)‐3‐(1‐iodo‐2‐phenyl‐2‐tosylvinyl)‐2‐phenyl‐1‐tosyl‐indole/(
)‐2‐phenyl‐3‐(2‐phenyl‐1‐(phenylselanyl)‐2‐tosylvinyl)‐1‐tosyl‐indole
derivatives
to
prepare
in
15–60
min
using
our
standard
reaction
conditions.
A
gram‐scale
experiment
as
well
postsynthetic
transformations
synthesized
were
performed
exhibit
advantages
this
synthetic
methodology.
Язык: Английский