Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(26)
Published: April 21, 2023
Abstract
A
homogeneous
manganese‐catalyzed
cross‐coupling
of
two
secondary
alcohols
for
the
divergent
synthesis
γ‐disubstituted
and
β‐disubstituted
ketones
is
reported.
Employing
well‐defined
Mn‐MACHO
Ph
as
catalyst,
this
novel
protocol
has
a
broad
substrate
scope
with
good
functional
group
tolerance
affords
diverse
library
valuable
disubstituted
in
moderate
to
yields.
The
strong
influence
reaction
temperature
on
selective
formation
alcohol
products
was
theorized
preliminary
DFT
studies.
Studies
have
shown
that
Gibbs
free
energy
thermodynamically
more
favourable
than
corresponding
at
lower
temperature.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(11), P. 4386 - 4464
Published: Jan. 1, 2022
The
emerging
field
of
organometallic
catalysis
has
shifted
towards
research
on
Earth-abundant
transition
metals
due
to
their
ready
availability,
economic
advantage,
and
novel
properties.
In
this
case,
manganese,
the
third
most
abundant
transition-metal
in
Earth's
crust,
emerged
as
one
leading
competitors.
Accordingly,
a
large
number
molecularly-defined
Mn-complexes
been
synthesized
employed
for
hydrogenation,
dehydrogenation,
hydroelementation
reactions.
regard,
catalyst
design
is
based
three
pillars,
namely,
metal-ligand
bifunctionality,
ligand
hemilability,
redox
activity.
Indeed,
developed
catalysts
not
only
differ
chelating
atoms
they
possess
but
also
working
principles,
thereby
different
turnover
numbers
product
molecules.
Hence,
critical
assessment
molecularly
defined
manganese
terms
atoms,
reaction
conditions,
mechanistic
pathway,
significant.
Herein,
we
analyze
complexes
catalytic
activity,
versatility
allow
multiple
transformations
routes
convert
substrates
target
This
article
will
be
helpful
get
significant
insight
into
design,
aiding
design.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(26)
Published: April 21, 2023
A
homogeneous
manganese-catalyzed
cross-coupling
of
two
secondary
alcohols
for
the
divergent
synthesis
γ-disubstituted
and
β-disubstituted
ketones
is
reported.
Employing
well-defined
Mn-MACHOPh
as
catalyst,
this
novel
protocol
has
a
broad
substrate
scope
with
good
functional
group
tolerance
affords
diverse
library
valuable
disubstituted
in
moderate
to
yields.
The
strong
influence
reaction
temperature
on
selective
formation
alcohol
products
was
theorized
preliminary
DFT
studies.
Studies
have
shown
that
Gibbs
free
energy
thermodynamically
more
favourable
than
corresponding
at
lower
temperature.
The Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
87(6), P. 3989 - 4000
Published: March 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,
Journal Year:
2023,
Volume and Issue:
88(9), P. 5944 - 5961
Published: April 13, 2023
A
Ru(II)-catalyzed
efficient
and
selective
N-alkylation
of
amines
by
C1-C10
aliphatic
alcohols
is
reported.
The
catalyst
[Ru(L1a)(PPh3)Cl2]
(1a)
bearing
a
tridentate
redox-active
azo-aromatic
pincer,
2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline
(L1a)
air-stable,
easy
to
prepare,
showed
wide
functional
group
tolerance
requiring
only
1.0
mol
%
(for
N-methylation
N-ethylation)
0.1
loading
for
with
C3-C10
alcohols.
array
N-methylated,
N-ethylated,
N-alkylated
were
prepared
in
moderate
good
yields
via
direct
coupling
1a
efficiently
catalyzes
the
diamines
selectively.
It
even
suitable
synthesizing
using
(aliphatic)
diols
producing
tumor-active
drug
molecule
MSX-122
yield.
excellent
chemo-selectivity
during
oleyl
alcohol
monoterpenoid
β-citronellol.
Control
experiments
mechanistic
investigations
revealed
that
1a-catalyzed
reactions
proceed
borrowing
hydrogen
transfer
pathway
where
removed
from
dehydrogenation
step
stored
ligand
backbone
1a,
which
subsequent
steps
transferred
situ
formed
imine
intermediate
produce
amines.
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.
Dalton Transactions,
Journal Year:
2024,
Volume and Issue:
53(7), P. 3236 - 3243
Published: Jan. 1, 2024
A
quinoline-based
pincer
Mn
catalyst
for
α-alkylation
of
methyl
ketones
using
primary
alcohols
as
alkyl
surrogates
is
presented.
The
C–C
bond
formation
reaction
proceeds
via
a
hydrogen
auto-transfer
protocol,
generating
water
the
only
by-product.
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.
