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.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(22), P. 16223 - 16241
Published: Aug. 23, 2024
The
utilization
of
earth-abundant,
cheap,
and
nontoxic
transition
metals
in
important
catalytic
transformations
is
essential
for
sustainable
development,
iron
has
gained
significant
attention
as
the
most
abundant
metal.
A
mixture
FeCl2
(3
mol
%),
phenanthroline
(6
KOtBu
(0.4
eqivalent)
was
used
an
effective
catalyst
sp3
C–H
alkylation
fluorene
using
alcohol
a
nonhazardous
alkylating
partner,
eco-friendly
water
formed
only
byproduct.
substrate
scope
includes
wide
range
substituted
fluorenes
benzyl
alcohols.
reaction
equally
with
challenging
secondary
alcohols
unactivated
aliphatic
Selective
mono-C9-alkylation
yielded
corresponding
products
good
isolated
yields.
Various
postfunctionalizations
C-9
alkylated
were
performed
to
establish
practical
utility
this
alkylation.
Control
experiments
suggested
homogeneous
path
involving
borrowing
hydrogen
mechanism
formation
subsequent
reduction
9-alkylidene
intermediate.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(8)
Published: Jan. 4, 2023
Abstract
A
convenient
PNP
pincer
manganese
catalyzed
transfer
hydrogenation
of
bromides
to
corresponding
debrominated
aryl
compounds
using
ethanol
as
the
hydrogen
sources
is
reported.
Importantly,
application
biomass‐derived
highlights
sustainability
methodology.
The
use
6‐phenyl
substituted
triazine‐based
P
i
pr
N
5
catalyst
allows
for
debromination
various
with
good
yields.
Notably,
process
also
occurs
derived
from
several
classes
natural
products
and
bioactive
compounds,
such
citronellol,
diacetone
fructose,
cholesterol,
vitamin
E.
Dalton Transactions,
Journal Year:
2022,
Volume and Issue:
51(38), P. 14734 - 14746
Published: Jan. 1, 2022
We
report
a
series
of
ruthenium
complexes
with
tetradentate
N,S-donor
ligand,
2,11-dithia[3.3](2,6)pyridinophane
(N2S2),
that
undergo
single
and
double
deprotonation
in
the
presence
base
leading
to
one
or
both
pyridine
rings.
Both
singly
doubly
deprotonated
were
structurally
characterized
by
single-crystal
X-ray
diffraction.
The
NMR
spectra
are
indicative
dearomatization
rings
upon
CH2-S
arm,
similar
phosphine-containing
pincer
ligands.
(N2S2)Ru
did
not
show
appreciable
catalytic
stoichiometric
reactivity
transfer
hydrogenation,
hydrogenation
dehydrogenation
alcohols,
attempted
activation
H2,
CO2,
other
substrates.
Such
lack
is
likely
due
low
stability
species
as
evident
from
structural
characterization
decomposition
products
which
shrinkage
macrocyclic
ring
occurs
via
picolyl
arm
migration.
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.
