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 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.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(29), С. 11789 - 11793
Опубликована: Март 18, 2020
Abstract
The
alkylation
of
amines
by
alcohols
is
a
broadly
applicable,
sustainable,
and
selective
method
for
the
synthesis
alkyl
amines,
which
are
important
bulk
fine
chemicals,
pharmaceuticals,
agrochemicals.
We
show
that
Cr
complexes
can
catalyze
this
C−N
bond
formation
reaction.
synthesized
isolated
35
examples
alkylated
including
13
previously
undisclosed
products,
use
amino
as
alkylating
agents
was
demonstrated.
catalyst
tolerates
numerous
functional
groups,
hydrogenation‐sensitive
examples.
Compared
to
many
other
alcohol‐based
amine
methods,
where
stoichiometric
amount
base
required,
our
Cr‐based
system
gives
yields
higher
than
90
%
various
with
catalytic
base.
Our
study
indicates
borrowing
hydrogen
or
autotransfer
reactions
could
thus
be
an
alternative
Fe,
Co,
Mn,
noble
metals
in
(de)hydrogenation
catalysis.
Organic Letters,
Год журнала:
2020,
Номер
22(5), С. 2064 - 2069
Опубликована: Фев. 24, 2020
An
iron-catalyzed
borrowing
hydrogen
strategy
has
been
applied
in
the
synthesis
of
β-branched
carbonyl
compounds.
Various
secondary
benzylic
and
aliphatic
alcohols
have
used
as
alkylating
reagents
under
mild
reaction
conditions.
The
ketones
isolated
good
to
excellent
yield.
Deuterium
labeling
experiments
provide
evidence
that
alcohol
is
hydride
source
this
no
reversible
step
or
hydrogen/deuterium
scrambling
takes
place
during
process.
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.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(9), С. 4607 - 4647
Опубликована: Янв. 1, 2024
This
review
collectively
discussed
the
utilisation
of
alcohols
in
various
organic
transformations
and
their
application
toward
intermediates
drugs,
drug
derivatives
natural
product-like
molecules.
Chemical Communications,
Год журнала:
2020,
Номер
56(60), С. 8376 - 8379
Опубликована: Янв. 1, 2020
Herein,
β-branched
carbonyl
compounds
were
synthesised
via
the
α-alkylation
of
ketones
with
secondary
alcohols
under
"borrowing
hydrogen"
catalysis.
A
wide
range
alcohols,
including
various
cyclic,
acyclic,
symmetrical,
and
unsymmetrical
have
been
successfully
applied
developed
reaction
conditions.
manganese(i)
complex
bearing
a
phosphine-free
multifunctional
ligand
catalysed
produced
water
as
sole
byproduct.
