Organometallics,
Год журнала:
2022,
Номер
41(6), С. 836 - 851
Опубликована: Март 9, 2022
A
series
of
symmetric
and
asymmetric
tetraaminocyclopentadienone
iron
tricarbonyl
complexes
were
prepared
from
Fe(CO)5
the
diaminoacetylenes
(DAA)
R2NC≡CNR2
(NR2
=
piperidinyl,
4-methylpiperidinyl,
homopiperidinyl)
via
intermediate
ferracyclobutenone
complexes.
In
presence
trimethylamine-N-oxide,
reactions
with
acetonitrile
afforded
corresponding
dicarbonyl
complexes,
which
served
as
highly
active
precatalysts
for
transfer
hydrogenation
aldehydes,
ketones,
imines
isopropanol
hydrogen
source
aldehydes
ketones
dihydrogen
under
comparatively
mild
reaction
conditions
(3
bar
H2
pressure,
room
temperature).
Density
functional
theory
(DFT)
calculations
performed
to
reveal
mechanism
isopropanol-mediated
benzaldehyde
acetophenone,
is
likely
involve
a
catalytically
hydroxycyclopentadienyl
hydride
species.
Dihydrogen
latter
onto
acetophenone
occurs
in
concerted
manner
exceptionally
low
activation
barriers
following
established
outer-sphere
mechanism.
ACS Central Science,
Год журнала:
2021,
Номер
7(4), С. 570 - 585
Опубликована: Март 25, 2021
Borrowing
hydrogen
is
a
process
that
used
to
diversify
the
synthetic
utility
of
commodity
alcohols.
A
catalyst
first
oxidizes
an
alcohol
by
removing
form
reactive
carbonyl
compound.
This
intermediate
can
undergo
diverse
range
subsequent
transformations
before
returns
"borrowed"
liberate
product
and
regenerate
catalyst.
In
this
way,
alcohols
may
be
as
alkylating
agents
whereby
sole
byproduct
one-pot
reaction
water.
recent
decades,
significant
advances
have
been
made
in
area,
demonstrating
many
effective
methods
access
valuable
products.
outlook
highlights
diversity
metal
biocatalysts
are
available
for
approach,
well
various
performed,
focusing
on
selection
most
advances.
By
succinctly
describing
conveying
versatility
borrowing
chemistry,
we
anticipate
its
uptake
will
increase
across
wider
scientific
audience,
expanding
opportunities
further
development.
Chemical Reviews,
Год журнала:
2024,
Номер
124(9), С. 6078 - 6144
Опубликована: Апрель 17, 2024
Alcohols
are
abundant
and
attractive
feedstock
molecules
for
organic
synthesis.
Many
methods
their
functionalization
require
them
to
first
be
converted
into
a
more
activated
derivative,
while
recent
years
have
seen
vast
increase
in
the
number
of
complexity-building
transformations
that
directly
harness
unprotected
alcohols.
This
Review
discusses
how
transition
metal
catalysis
can
used
toward
this
goal.
These
broadly
classified
three
categories.
Deoxygenative
functionalizations,
representing
derivatization
C–O
bond,
enable
alcohol
act
as
leaving
group
formation
new
C–C
bonds.
Etherifications,
characterized
by
O–H
represent
classical
reactivity
has
been
modernized
include
mild
reaction
conditions,
diverse
partners,
high
selectivities.
Lastly,
chain
reactions
described,
wherein
acts
mediator
formal
C–H
alkyl
backbone.
Each
these
classes
transformation
will
discussed
context
intermolecular
arylation,
alkylation,
related
reactions,
illustrating
alcohols
harnessed
Chemistry - A European Journal,
Год журнала:
2020,
Номер
26(57), С. 12912 - 12926
Опубликована: Апрель 16, 2020
Abstract
Hydrogen‐borrowing
catalysis
represents
a
powerful
method
for
the
alkylation
of
amine
or
enolate
nucleophiles
with
non‐activated
alcohols.
This
approach
relies
upon
catalyst
that
can
mediate
strategic
series
redox
events,
enabling
formation
C−C
and
C−N
bonds
producing
water
as
sole
by‐product.
In
majority
cases
these
reactions
have
been
employed
to
target
achiral
racemic
products.
contrast,
focus
this
Minireview
is
hydrogen‐borrowing‐catalysed
in
which
absolute
stereochemical
outcome
process
be
controlled.
Asymmetric
hydrogen‐borrowing
rapidly
emerging
synthesis
enantioenriched
carbonyl
containing
products
examples
involving
both
bond
are
presented.
A
variety
different
approaches
discussed
including
use
chiral
auxiliaries,
asymmetric
enantiospecific
processes.
Organic Letters,
Год журнала:
2021,
Номер
23(3), С. 869 - 875
Опубликована: Янв. 21, 2021
Herein,
a
phosphine-free
pincer
ruthenium(III)
catalyzed
β-alkylation
of
secondary
alcohols
with
primary
to
α-alkylated
ketones
and
two
different
β-branched
are
reported.
Notably,
this
transformation
is
environmentally
benign
atom
efficient
H2O
H2
gas
as
the
only
byproducts.
The
protocol
extended
gram-scale
reaction
for
functionalization
complex
vitamin
E
cholesterol
derivatives.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(26)
Опубликована: Апрель 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.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(33), С. 23338 - 23347
Опубликована: Авг. 6, 2024
A
single-atom
iron
catalyst
was
found
to
exhibit
exceptional
reactivity
in
acceptorless
dehydrogenative
coupling
for
quinoline
synthesis,
outperforming
known
homogeneous
and
nanocatalyst
systems.
Detailed
characterizations,
including
aberration-corrected
HAADF-STEM,
XANES,
EXAFS,
jointly
confirmed
the
presence
of
atomically
dispersed
centers.
Various
functionalized
quinolines
were
efficiently
synthesized
from
different
amino
alcohols
a
range
ketones
or
alcohols.
The
achieved
turnover
number
(TON)
up
10
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.
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
The Journal of Organic Chemistry,
Год журнала:
2020,
Номер
85(23), С. 15396 - 15405
Опубликована: Ноя. 2, 2020
The
iron-catalyzed
hydrogen
transfer
strategy
has
been
applied
to
the
redox
condensation
of
o-hydroxynitrobenzene
with
alcohol,
leading
formation
benzoxazole
derivatives.
A
wide
range
2-substituted
benzoxazoles
were
synthesized
in
good
excellent
yields
without
addition
an
external
agent.
series
control
experiments
provided
a
plausible
mechanism.
Furthermore,
reaction
system
was
successfully
extended
synthesis
benzothiazoles
and
benzimidazoles.
