ChemCatChem,
Год журнала:
2020,
Номер
13(3), С. 934 - 939
Опубликована: Ноя. 19, 2020
Abstract
We
herein
report
the
catalytic
hydrogenation
of
carbonates
and
polycarbonates
into
their
corresponding
diols/alcohols
using
well‐defined,
air‐stable,
high‐valent
cobalt
complexes.
Several
novel
Cp*Co(III)
complexes
bearing
N
,
O
‐chelation
were
isolated
for
first
time
structurally
characterized
by
various
spectroscopic
techniques
including
single
crystal
X‐ray
crystallography.
These
Co(III)
have
shown
excellent
activity
to
produce
value
added
from
carbonate
through
molecular
hydrogen
as
sole
reductant
or
i
PrOH
transfer
source.
To
demonstrate
developed
methodology's
practical
applicability,
we
recycled
bisphenol
A
monomer
compact
disc
(CD)
under
established
reaction
conditions
phosphine‐free,
earth‐abundant,
air‐
moisture‐stable
catalysts.
ACS Catalysis,
Год журнала:
2020,
Номер
10(14), С. 8023 - 8031
Опубликована: Июнь 26, 2020
Oxindoles
have
been
successfully
α-alkylated
under
Cp*CoIII
catalysis
by
a
vast
array
of
secondary
alcohols,
including
cyclic,
acyclic,
symmetrical,
and
unsymmetrical,
to
produce
C-alkylated
oxindoles.
This
protocol
was
also
extended
the
α-alkylation
N,N-dimethyl
barbituric
acid
benzyl
cyanides.
The
kinetic
profile
other
preliminary
mechanistic
investigations
suggest
first-order
reaction
rate
in
oxindoles
catalysts.
A
plausible
catalytic
cycle
is
proposed
on
basis
profile,
investigations,
previous
studies
similar
transformations,
whereas
density
functional
theory
calculations
provide
insight
into
nature
active
species.
Catalysis Science & Technology,
Год журнала:
2022,
Номер
12(15), С. 4753 - 4762
Опубликована: Янв. 1, 2022
β-Alkylation
of
alcohols
has
been
efficiently
accomplished
using
readily
available
3d
metal
Cr
under
microwave
conditions
in
air.
Well-defined
molecular
is
involved
with
a
KIE
7.33
and
insertion
α-alkylated
ketone
into
Cr–H
bond
as
the
RDS.
Organic Letters,
Год журнала:
2022,
Номер
24(33), С. 6219 - 6223
Опубликована: Авг. 12, 2022
A
mild,
environmentally
benign
approach
for
α-methylation
of
ketones
utilizing
methanol
as
the
C1
source
under
visible
light
has
been
developed.
The
reaction
conditions
were
favorable
a
wide
range
with
both
aromatic
and
aliphatic
backbones,
allowing
good-to-excellent
yields
respective
products.
tentative
mechanism
is
postulated
after
preliminary
mechanistic
kinetic
experiments.
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(18), С. 3100 - 3121
Опубликована: Июль 4, 2022
Abstract
The
alkylation
of
ketones
or
secondary
alcohols
using
as
alkylating
agents
via
hydrogen
borrowing
strategy
presents
a
powerful
method
for
the
synthesis
ɑ‐alkylated
ketones.
In
this
review,
we
summarize
progress
catalyzed
by
Ir,
Pd,
Rh,
Ru,
Mn,
Fe,
Co,
Ni,
and
Cu
catalysts
α‐alkylation
with
cross‐coupling
from
2017
to
2021.
A
wide
range
(aromatic
aliphatic
ketones)
(benzylic
primary
alcohols,
aromatic
alkenyl
diols)
are
well
tolerated.
Furthermore,
also
discuss
current
challenges
propose
perspectives
on
coming
development
in
filed.
objective
present
review
is
give
an
overview
recent
advances
β‐alkylation
alcohols.
Finally,
hope
that
will
inspirations
magnified
image
Organic Letters,
Год журнала:
2019,
Номер
21(18), С. 7420 - 7423
Опубликована: Сен. 3, 2019
A
homogeneous
cobalt-catalyzed
β-alkylation
of
secondary
alcohols
with
primary
to
selectively
synthesize
ketones
via
acceptorless
dehydrogenative
coupling
is
reported
for
the
first
time.
Notably,
this
transformation
environmentally
benign
and
atom
economical
water
hydrogen
gas
as
only
byproducts.
Organic Letters,
Год журнала:
2020,
Номер
22(20), С. 7879 - 7884
Опубликована: Окт. 1, 2020
An
assortment
of
aromatic
ketones
was
successfully
functionalized
with
a
variety
unactivated
secondary
alcohols
that
serve
as
alkylating
agents,
providing
β-disubstituted
ketone
products
in
good
to
excellent
yields.
Remarkably,
challenging
substrates
such
simple
acetophenone
derivatives
are
effectively
alkylated
under
this
ruthenium
catalysis.
The
substituted
cyclohexanol
compounds
displayed
product-induced
diastereoselectivity.
Mechanistic
studies
indicate
the
involvement
hydrogen-borrowing
pathway
these
alkylation
reactions.
Notably,
selective
and
catalytic
C-C
bond-forming
reaction
requires
only
minimal
load
catalyst
base
produces
H2O
byproduct,
making
protocol
attractive
environmentally
benign.
Chemistry - A European Journal,
Год журнала:
2021,
Номер
27(41), С. 10737 - 10748
Опубликована: Май 17, 2021
Abstract
A
Cp*Ir(III)
complex
(
1
)
of
a
newly
designed
ligand
L
featuring
proton‐responsive
pyridyl(benzamide)
appended
on
N
‐
heterocyclic
carbene
(NHC)
has
been
synthesized.
The
molecular
structure
reveals
dearomatized
form
the
ligand.
protonation
with
HBF
4
in
tetrahydrofuran
gives
corresponding
aromatized
[Cp*Ir(L
H)Cl]BF
2
).
Both
compounds
are
characterized
spectroscopically
and
by
X‐ray
crystallography.
acid
is
examined
H
NMR
UV‐vis
spectra.
character
exploited
for
catalyzing
α
‐alkylation
ketones
β
secondary
alcohols
using
primary
as
alkylating
agents
through
hydrogen‐borrowing
methodology.
Compound
an
effective
catalyst
these
reactions
exhibits
superior
activity
comparison
to
structurally
similar
iridium
)Cl]PF
6
3
lacking
pendant
amide
moiety.
catalytic
alkylation
wide
substrate
scope,
low
base
loadings,
short
reaction
time.
efficacy
also
demonstrated
syntheses
quinoline
lactone
derivatives
via
acceptorless
dehydrogenation,
selective
two
steroids,
pregnenolone
testosterone.
Detailed
mechanistic
investigations
DFT
calculations
substantiate
role
process.
Organic Letters,
Год журнала:
2022,
Номер
24(30), С. 5584 - 5589
Опубликована: Июль 27, 2022
We
report
a
visible-light-induced
iron-catalyzed
α-alkylation
of
ketones.
The
photocatalytic
system
is
based
on
the
single
diaminocyclopentadienone
iron
tricarbonyl
complex.
Two
catalytic
intermediates
this
complex
are
able
to
harvest
light,
allowing
synthesis
substituted
aromatic
and
aliphatic
ketones
at
room
temperature
using
borrowing
hydrogen
strategy
in
presence
various
primary
alcohols
as
alkylating
reagents.
Preliminary
mechanistic
studies
unveil
role
light
for
both
dehydrogenation
reduction
step.
