Chemistry - A European Journal,
Год журнала:
2022,
Номер
28(62)
Опубликована: Июль 12, 2022
The
precise
control
of
monomer
sequence
and
stereochemistry
in
copolymerization
is
much
interest
importance
for
the
synthesis
high
performance
materials,
but
studies
toward
this
goal
have
met
with
only
limited
success
to
date.
coordination
polymerization
diphenylphosphinostyrene
(p-StPPh2
o-StPPh2
)
its
styrene
(St)
by
(C5
Me4
SiMe3
)Sc(CH2
C6
H4
NMe2
-o)2
been
achieved
first
time
afford
a
new
series
phosphine
functionalized
syndiotactic
polystyrene.
By
design
polymer
structure,
copolymer
St
(poly(o-StPPh2
-alt-St)-b-sPS)
containing
atactic
alternating
block
polystyrene
(sPS)
showed
excellent
thermal
stability
chemical
resistance.
simple
combination
triphenylphosphine
realized
stable
immobilization
metal
nanoparticles
highly
robust
metal@poly(o-StPPh2
-alt-St)-b-sPS
nanocatalysts
at
temperature
various
atmospheres.
Cu@poly(o-StPPh2
catalyst
can
serve
as
efficient
heterogeneous
quinoline
derivatives
acceptorless
dehydrogenative
coupling
o-aminobenzylalcohol
ketones.
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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(13)
Опубликована: Фев. 1, 2024
Abstract
The
synthesis
of
mono‐
N
‐methylated
aliphatic
primary
amines
has
traditionally
been
challenging,
requiring
noble
metal
catalysts
and
high‐pressure
H
2
for
achieving
satisfactory
yields
selectivity.
Herein,
we
developed
an
approach
the
selective
coupling
methanol
amines,
without
hydrogen,
using
a
manganese‐based
catalyst.
Remarkably,
up
to
98
%
with
broad
substrate
scope
were
achieved
at
low
catalyst
loadings.
Notably,
due
weak
base‐catalyzed
alcoholysis
formamide
intermediates,
our
novel
protocol
not
only
obviates
addition
but
also
prevents
side
secondary
‐methylation,
supported
by
control
experiments
density
functional
theory
calculations.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(26)
Опубликована: Фев. 14, 2024
Abstract
This
review
provides
a
comprehensive
overview
of
mono‐alkylation
methodologies
targeting
crucial
nitrogen
moieties
–
amines,
amides,
and
sulfonamides
found
in
organic
building
blocks
pharmaceuticals.
Emphasizing
the
intersection
chemical
precision
with
drug
discovery,
central
challenge
addressed
is
achieving
one‐pot
mono‐selective
short‐chain
N‐alkylations
(methylations,
ethylations,
n
‐propylations),
preventing
undesired
overalkylation.
Additionally,
sustainable,
safe,
benign
alternatives
to
traditional
alkylating
agents,
including
alcohols,
carbon
dioxide,
carboxylic
acids,
nitriles,
alkyl
phosphates,
quaternary
ammonium
salts,
carbonates,
are
explored.
review,
categorized
by
nature
agent,
aids
researchers
selecting
suitable
methods
for
N‐alkylation.
Green Chemistry,
Год журнала:
2022,
Номер
24(15), С. 5965 - 5977
Опубликована: Янв. 1, 2022
Heterogeneous
non-noble
bimetallic
CuCo
nanoparticle
catalysts
for
selective
N
-monomethylation
and
,
-dimethylation
reactions
under
base-free
conditions,
offering
>50
examples
from
aromatic/aliphatic
amines,
nitrocompounds
different
alcohols.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(13)
Опубликована: Фев. 1, 2024
Abstract
The
synthesis
of
mono‐
N
‐methylated
aliphatic
primary
amines
has
traditionally
been
challenging,
requiring
noble
metal
catalysts
and
high‐pressure
H
2
for
achieving
satisfactory
yields
selectivity.
Herein,
we
developed
an
approach
the
selective
coupling
methanol
amines,
without
hydrogen,
using
a
manganese‐based
catalyst.
Remarkably,
up
to
98
%
with
broad
substrate
scope
were
achieved
at
low
catalyst
loadings.
Notably,
due
weak
base‐catalyzed
alcoholysis
formamide
intermediates,
our
novel
protocol
not
only
obviates
addition
but
also
prevents
side
secondary
‐methylation,
supported
by
control
experiments
density
functional
theory
calculations.
Abstract
N
‐alkyl
anilines
are
a
series
of
common
and
versatile
compounds
which
not
only
have
been
used
as
reaction
solvents,
acid‐accepters,
organic‐bases,
but
also
in
synthesis
dyes,
pharmaceuticals,
anti‐colodal.
The
‐methyl
and/or
,
‐dimethyl
the
most
representative
ones
among
these.
Due
to
their
widespread
uses,
numerous
works
reported
on
synthetic
strategies
past
decades.
studies
N−H
methylations
mainly
focus
selection
reagents,
catalysts,
or
ligands
design.
Different
transition‐metals,
e.
g.,
Ir,
Ru,
Pd,
et.
al,
with
different
methylation
protocols.
Methanol
(CH
3
OH),
carbon
dioxide
(CO
2
),
formaldehyde
(HCHO),
dimethyl
carbonate
((CH
)
CO
was
C
source,
hydrogen
(H
silanes
H
source.
In
this
work,
we
would
like
summarize
latest
advances
(
included)
derivatives.
This
review
provides
an
overview
reactants
catalyst,
well
emphasis
scope
substrates
proposed
mechanism
for
each
work.
