Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
134(38)
Published: July 22, 2022
Abstract
A
facile
benzylic
alkylation
of
indenes
and
other
arenes
was
developed
from
readily
available
primary
secondary
alcohols
using
our
newly
investigated
CCC
pincer
Ir
III
catalyst
(SNIr−H).
Excellent
regioselectivity
yield
(89
%)
the
C3‐alkylated
were
obtained.
Additionally,
challenging
sp
2
C‐alkylation
accomplished.
This
method
could
be
utilized
for
synthesis
analogs
a
histamine
H1
receptor
antagonist
functional
material
template
molecule,
indeno[2,1‐a]indene.
hemilabile
‐dihydride
intermediate
proposed
based
on
control
experiments
previous
density
theory
(DFT)
calculations
borrowing
hydrogen
mechanism
is
key
to
success
this
in
reduction
unactivated
multi‐substituted
olefin
intermediates.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(3), P. 1910 - 1926
Published: Jan. 11, 2024
Herein,
employing
well-defined
redox
noninnocent
cobalt(II)
complexes
an
efficient
sp3
C–H
alkylation
of
fluorenes
using
alcohols
as
alkylating
agents
to
result
in
alkylated
is
reported.
The
catalytic
protocol
was
versatile
with
various
and
benzyl
alcohols.
It
also
showed
very
good
functional
group
tolerance
both
fluorenes.
Moreover,
single-step
simultaneous
di
C–C
well
the
C–N
reaction
observed
this
protocol.
Such
selective
dialkylation
indeed
beneficial.
Several
control
experiments,
deuterium
labeling,
1H
NMR
kinetic
studies
have
revealed
a
ligand
radical-based
borrowing
hydrogen
mechanism
involving
azo-aromatic
cobalt
catalysts
for
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.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(11), P. 6729 - 6736
Published: May 23, 2022
We
report
a
ruthenium-catalyzed
tandem
Guerbet–alkylation
strategy
for
the
valorization
of
ethanol.
The
products
ethanol
upgrading
(higher-order
alcohols)
undergo
subsequent
C–C
bond
forming
reactions
with
four
carbon
pronucleophiles
and
one
ylide.
Studies
into
catalyst
design
led
to
development
ClRu(5-Mebpi)(PPh3)2
(bpi
=
1,3-bis(2′-pyridylimino)isoindolate)
as
highly
efficient
producing
biofuels
value-added
chemicals
from
via
Guerbet
reactions.
This
affords
65%
higher-order
alcohols
in
short
reaction
times
(2
h),
providing
highest
TON
(155,890)
TOF
(12,690
h–1)
homogeneous
reported
date.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(8), P. 1305 - 1309
Published: Feb. 17, 2023
The
present
study
demonstrates
the
first
transition-metal-free
catalytic
C-alkylation
via
a
borrowing
hydrogen
pathway
for
α-alkylation
of
ketone,
synthesis
substituted
quinoline,
and
9-monoalkylation
fluorene.
With
applications
on
diversification
biologically
active
molecules
gram-scale
synthesis,
preliminary
investigation
reaction
mechanism
has
been
carried
out,
suggesting
radical-mediated
pathway.
Organic & Biomolecular Chemistry,
Journal Year:
2022,
Volume and Issue:
20(41), P. 7998 - 8030
Published: Jan. 1, 2022
This
review
focuses
on
the
Ru-catalyzed
de(hydrogenative)
formation
of
C–C
and
CC
bonds.
The
comparative
reactivity
different
Ru-complexes
to
gain
selectivity
in
product
is
presented,
together
with
brief
mechanistic
insights.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(4), P. 2612 - 2620
Published: Feb. 1, 2023
An
external
photocatalyst-free
benzylic
C-H
functionalization
with
fluorenones
under
visible-light
irradiation
has
been
achieved.
This
transformation
provides
an
efficient
synthetic
approach
to
9-benzylated
fluorenols
in
≤91%
yield
100%
atom
economy
mild
conditions.
Spectroscopic
studies
suggest
that
a
reductive
quenching
of
photoexcited
toluene
derivatives
generates
ketyl
radicals
and
benzyl
radicals,
which
undergo
cross-coupling
afford
the
desired
fluorenols.
