Russian Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
93(6), P. RCR5123 - RCR5123
Published: June 1, 2024
Free
alcohols
are
ubiquitous
in
nature,
drugs,
bulk
chemicals,
and
various
complex
molecules.
The
abundantly
available
free
aliphatic
alcohols,
being
inexpensive,
sustainable
starting
materials
organic
synthesis
to
construct
value-added
scaffolds.
Direct
C(sp<sup>3</sup>)–H
functionalization
of
inert
bonds
alcoholic
chain
is
challenging
due
their
inactive
nature
towards
chemical
reactions
also
multiple
similar
C–H
for
reaction
at
a
time.
Barton
process,
which
classical
method
generating
alkoxyl
radicals,
has
been
widely
used
the
remote
using
strategy
1,5-hydrogen
atom
transfer
(1,5-HAT).
However,
requirement
pre-activation
not
only
adds
extra
tedious
steps
but
also,
these
precursors
prepare
handle.
Generating
desired
radicals
from
difficult
task
affects
economy
reactions.
Numerous
methods
covering
unprotected
non-activated
diverse
(α-,
β-,
γ-,
δ-)
positions
access
functionalized
elaborated
here.
A
precise
focused
compilation
will
help
understand
what
established
how
new
methodologies
can
be
developed
future
needs.
<br>
bibliography
includes
158
references.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(9), P. 6078 - 6144
Published: April 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
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 3, 2025
Optically
pure
1,2-diols
and
1,3-diols
are
the
most
privileged
structural
motifs,
widely
present
in
natural
products,
pharmaceuticals
chiral
auxiliaries
or
ligands.
However,
their
synthesis
relies
on
use
of
toxic
expensive
metal
catalysts
suffer
from
low
regioselectivity.
Catalytic
asymmetric
optically
1,n-diols
bulk
chemicals
a
highly
stereoselective
atom-economical
manner
remains
formidable
challenge.
Here,
we
disclose
versatile
modular
method
for
enantioenriched
high-production-volume
ethane-1,2-diol
(MEG)
1,3-propanediol
(PDO),
respectively.
The
key
to
success
is
temporarily
mask
diol
group
as
an
acetonide,
which
imparts
selectivity
step
C(sp3)-H
functionalization.
Additionally,
containing
two
stereogenic
centers
also
prepared
through
diastereoselective
late-stage
functionalization
biological
active
compounds
expedient
ligands
pharmaceutically
relevant
molecules
further
highlight
synthetic
potential
this
protocol.
authors
report
ethylene
glycol
1,3-propanediol,
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(21)
Published: Feb. 27, 2024
Chiral
trisubstituted
vicinal
diols
are
a
type
of
important
organic
compounds,
serving
as
both
common
structure
units
in
bioactive
natural
products
and
chiral
auxiliaries
asymmetric
synthesis.
Herein,
by
using
siloxypropadienes
the
precursors
allyl
copper(I)
species,
copper(I)-catalyzed
diastereoselective
enantioselective
reductive
allylation
ketones
was
achieved,
providing
syn-diols
anti-diols
good
to
excellent
enantioselectivity.
DFT
calculations
show
that
cis-γ-siloxy-allyl
copper
species
generated
favorably
with
either
1-TBSO-propadiene
or
1-TIPSO-propadiene.
Moreover,
steric
difference
TBS
group
TIPS
distinguishes
face
selectivity
acetophenone,
leading
syn-selectivity
for
anti-selectivity
Easy
transformations
were
performed,
demonstrating
synthetic
utility
present
method.
one
diol
prepared
above
used
suitable
organocatalyst
catalytic
self-coupling
aldimines
situ
B
Synthesis,
Journal Year:
2023,
Volume and Issue:
55(10), P. 1487 - 1496
Published: Feb. 20, 2023
Abstract
The
evolution
of
methods
for
carbonyl
allylation
and
crotylation
alcohol
proelectrophiles
culminating
in
the
design
iodide-bound
ruthenium-JOSIPHOS
catalysts
is
prefaced
by
a
brief
historical
perspective
on
asymmetric
its
relevance
to
polyketide
construction.
Using
gaseous
allene
or
butadiene
as
precursors
allyl-
crotylruthenium
nucleophiles,
respectively,
new
capabilities
have
been
unlocked,
including
stereo-
site-selective
1,3-diols
related
polyols.
1
Introduction
Historical
Perspective
2
Ruthenium-Catalyzed
Conversion
Lower
Alcohols
into
Higher
3
Conclusion
Future
Outlook
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(15)
Published: Feb. 8, 2024
Abstract
Selective
functionalization
of
allenic
C(sp
2
)‐H
is
an
ideal
approach
to
upgrading
simple
allenes
synthetically
useful
allenes,
albeit
suffering
from
challenges
associated
with
inert
reactivity
and
inferior
selectivity.
Inspired
by
energy
chemistry,
a
catalytic
hydrogen
evolution
reaction
(HER)
strategy
was
leveraged
selectively
activate
weakly
acidic
allene
bonds
in
reductive
mode.
An
array
[Co
O
]
metallacycle
complexes
were
readily
devised
starting
amino
acids,
they
demonstrated
as
robust
HER
catalysts,
which
would
break
release
hydrogen.
With
the
newly
developed
catalyst,
regioselective
electrochemical
alcoholic
α
3
unprecedentedly
achieved.
This
features
excellent
regioselectivity,
unconventional
chemoselectivity,
good
functional‐group
tolerance
(62
examples),
mild
conditions.
Mechanism
experiments
revealed
reactive
hydroxy‐coordinated
cobalt(II)
species
reaction.
Density
functional
theory
(DFT)
calculations
also
conducted
rationalize
regioselectivity
observed
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(12), P. 7905 - 7914
Published: March 13, 2024
Experimental
and
computational
studies
illuminating
the
factors
that
guide
metal-centered
stereogenicity
and,
therefrom,
selectivity
in
transfer
hydrogenative
carbonyl
additions
of
alcohol
proelectrophiles
catalyzed
by
chiral-at-metal-and-ligand
octahedral
d6
metal
ions,
iridium(III)
ruthenium(II),
are
described.
To
augment
or
invert
regio-,
diastereo-,
enantioselectivity,
predominantly
one
from
among
as
many
15
diastereomeric-at-metal
complexes
is
required.
For
catalysts,
cyclometalation
assists
defining
stereocenter,
for
ruthenium(II)
iodide
counterions
play
a
key
role.
Whereas
classical
strategies
to
promote
catalysis
aim
high-symmetry
transition
states,
well-defined
low-symmetry
states
can
unlock
selectivities
otherwise
difficult
achieve
inaccessible.
ChemistrySelect,
Journal Year:
2024,
Volume and Issue:
9(1)
Published: Jan. 2, 2024
Abstract
Solar‐driven
hydrogen
(H
2
)
evolution
combined
with
synchronously
selective
oxidation
for
fine
chemicals
production
is
of
great
significance
in
energy
and
synthetic
chemistry.
Herein,
ultrafine
Pd
nanoparticles‐encapsulated
MIL‐100(Fe)
(Pd‐MOF‐Fe)
nanocomposites
are
synthesized
through
double‐solvent
impregnation
integrated
photo‐reduction
method.
Integrating
MOF‐based
catalysis
Pd‐based
catalysis,
the
Pd‐MOF‐Fe
can
serve
as
multifunctional
catalyst
photoinduced
alcohol
dehydrogenation
reaction.
Optimal
generation
rates
H
(3.61
mmol
g
−1
h
benzaldehyde
(3.40
gained
over
Pd‐MOF‐Fe,
ca.
4.1
times
that
Pd/MOF‐Fe,
which
crystals
size
ranging
from
3
to
6
nm
immobilized
on
intersurface
MOFs.
Besides,
controlled
experiments
reveal
pivotal
role
opened
FeO
nodes
Lewis
acid
sites
toward
activation.
This
work
provides
a
controllable
approach
metal
nanoparticle
immobilization.
Furthermore,
considering
diversified
MOF
structures,
this
study
also
highlights
infinite
possibility
nanoparticle/MOFs
platform
solar
conversion
production.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 6, 2024
Catalytic
enantioselective
hydrogen
autotransfer
reactions
for
the
direct
conversion
of
lower
alcohols
to
higher
are
catalogued
and
their
application
total
synthesis
polyketide
natural
products
is
described.
These
methods
exploit
a
redox
process
in
which
alcohol
oxidation
balanced
by
reductive
generation
organometallic
nucleophiles
from
unsaturated
hydrocarbon
pronucleophiles.
Unlike
classical
carbonyl
additions,
premetalated
reagents,
chiral
auxiliaries
discrete
alcohol-to-aldehyde
not
required.
Additionally,
chemoselective
dehydrogenation
primary
presence
secondary
enables
C-C
coupling
absence
protecting
groups.