Dalton Transactions,
Год журнала:
2022,
Номер
51(11), С. 4354 - 4365
Опубликована: Янв. 1, 2022
Indolyl
fragment
containing
phenanthroline
based
new
ligands
and
their
corresponding
Ru(II)
complexes
were
synthesized
fully
characterized
by
various
spectroscopic
techniques.
The
catalytic
activity
of
these
newly
cyclometalated
(NNC)Ru(II)
was
explored
towards
the
β-methylation
alcohols
using
methanol.
Notably,
displayed
superior
reactivity
compared
to
(NNN)Ru(II)
complexes.
Utilizing
this
strategy,
a
wide
range
primary,
secondary,
aliphatic
straight
chain
selectively
methylated.
This
protocol
further
employed
for
methylation
few
natural
products
gram
scale
synthesis
β-methylated
alcohols.
A
series
control
experiments
kinetic
studies
performed
understand
plausible
reaction
mechanism.
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
ACS Catalysis,
Год журнала:
2023,
Номер
13(22), С. 15013 - 15053
Опубликована: Ноя. 6, 2023
Methanol
is
a
fundamental
feedstock
and
widely
used
in
the
chemical
petroleum
industries.
It
can
serve
as
C1
source
to
make
variety
of
C–C
C–N
bond
formation
dehydrogenative
coupling
products,
which
have
important
applications
natural
products
drug
discovery.
A
high
hydrogen
content
(12.5
wt%)
methanol
makes
it
an
effective
H2
donor
for
transfer
hydrogenation
various
reducible
functional
groups.
plethora
transition
metal-based
processes
been
developed
using
methanol.
Notably,
recent
review
articles
focused
on
aspect
However,
more
updated
that
examines
challenges
both
C1-source
H2-source
organic
transformations
contributing
concept
economy
has
not
presented
yet.
This
Review
summarizes
(homogeneous,
heterogeneous,
photo-)
catalyst
system
C-,
N-,
O-methylation
ketones,
alcohols,
amides,
nitriles,
heterocyclic
compounds,
sulfones,
amines,
sulfonamides
direct
N-methylation
nitro
compounds
under
borrowing
strategy
N-formylation
amines
acceptorless
dehydrogenation
source.
also
covers
insights
into
reaction
mechanisms
role
carefully
selected
ligands
metal
catalysis
activation
incorporation
-CD3,
methylation
molecules.
Moreover,
describes
groups
such
aldehydes,
alkynes,
with
detail.
ACS Catalysis,
Год журнала:
2023,
Номер
13(7), С. 4231 - 4249
Опубликована: Март 13, 2023
In
the
past
few
decades,
advances
of
CO2
reduction
have
been
mostly
focused
on
synthesis
C1
products,
such
as
CO,
formic
acid,
methanol,
and
methane.
However,
syntheses
C2+
products
from
generally
abundant
sources
CO2,
CH4
are
traditionally
more
difficult
because
they
involve
two
selective
processes:
activation
source
simultaneous
C–C
bond
formation.
Recent
in
organometallic
chemistry
catalysis
provide
effective
means
for
chemical
transformation
to
higher-energy
under
mild
conditions.
Moreover,
recent
expansion
these
mechanistically
different
methods
has
enabled
use
various
undergo
either
homocoupling
or
heterocoupling
via
formation
generate
products.
this
review,
we
systematically
present
conversions
homogeneous
catalysis.
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.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(9), С. 5944 - 5961
Опубликована: Апрель 13, 2023
A
Ru(II)-catalyzed
efficient
and
selective
N-alkylation
of
amines
by
C1-C10
aliphatic
alcohols
is
reported.
The
catalyst
[Ru(L1a)(PPh3)Cl2]
(1a)
bearing
a
tridentate
redox-active
azo-aromatic
pincer,
2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline
(L1a)
air-stable,
easy
to
prepare,
showed
wide
functional
group
tolerance
requiring
only
1.0
mol
%
(for
N-methylation
N-ethylation)
0.1
loading
for
with
C3-C10
alcohols.
array
N-methylated,
N-ethylated,
N-alkylated
were
prepared
in
moderate
good
yields
via
direct
coupling
1a
efficiently
catalyzes
the
diamines
selectively.
It
even
suitable
synthesizing
using
(aliphatic)
diols
producing
tumor-active
drug
molecule
MSX-122
yield.
excellent
chemo-selectivity
during
oleyl
alcohol
monoterpenoid
β-citronellol.
Control
experiments
mechanistic
investigations
revealed
that
1a-catalyzed
reactions
proceed
borrowing
hydrogen
transfer
pathway
where
removed
from
dehydrogenation
step
stored
ligand
backbone
1a,
which
subsequent
steps
transferred
situ
formed
imine
intermediate
produce
amines.
