ChemCatChem,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 8, 2024
Abstract
The
selective,
transition
metal‐free
hydrosilylation
of
CO
2
to
CH
(OSiEt
3
)
has
been
achieved
under
mild
conditions
and
in
high
isolated
yields
(up
90%)
by
using
Et
SiH
the
simple,
easily
prepared
borohydride
catalyst
Li
+
[HB(C
6
F
5
]
−
.
resulting
‐derived
bis(silyl)acetal
product—whose
mechanism
formation
interrogated
through
detailed
computational
experimental
studies—can
be
rapidly
valorized
facile
synthesis
N
‐heterocyclic
carbenes,
via
their
corresponding
imidazolium
salts.
By
relatively
inexpensive,
isotopically
enriched
13
this
protocol
can
exploited
prepare
NHC
isotopologues
that
are
selectively
C
labelled
at
key,
ligating
C2
position.
This
provides
an
electronically
responsive
NMR
spectroscopic
handle
with
dramatically
enhanced
sensitivity,
which
directly
benefit
reactivity
studies
both
organo‐
organometallic
catalysis,
where
use
is
ubiquitous.
Bulletin of the Chemical Society of Japan,
Journal Year:
2023,
Volume and Issue:
96(7), P. 693 - 701
Published: June 8, 2023
Abstract
Carbon
dioxide
(CO2)
is
not
only
a
greenhouse
gas
but
also
renewable
carbon
source
for
organic
synthesis.
Here
we
have
summarized
our
studies
on
the
conversions
of
CO2
into
value-added
chemicals
via
cooperative
catalysis
using
multifunctional
catalysts.
For
example,
bifunctional
metalloporphyrin
catalysts
with
quaternary
ammonium
halides
were
developed
selective
synthesis
cyclic
carbonates
or
polycarbonates
from
epoxides
and
CO2.
Bifunctional
MgII
ZnII
porphyrins
showed
high
catalytic
activity
carbonates,
while
AlIII
catalyzed
copolymerization
cyclohexene
oxide
to
give
poly(cyclohexene
carbonate).
The
activities
resulted
action
central
metal
ion
salts.
Chiral
kinetic
resolution
terminal
internal
developed.
In
addition,
macrocyclic
multinuclear
complex
Zn5L3,
which
was
synthesized
by
self-assembly
Zn(OAc)2
BINOL
derivative
(L),
reduction
phenylsilane
produce
various
useful
synthetic
intermediates
compounds.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(6), P. 877 - 883
Published: March 1, 2023
The
solvent-free
N-formylation
of
2-(methylamino)pyridine
with
CO2
and
phenylsilane
was
catalyzed
by
Cu(OAc)2
alone
to
give
N-methyl-N-(2-pyridyl)formamide
called
Comins-Meyers
formamide.
X-ray
crystallographic
analysis
a
copper
complex
revealed
paddle-wheel
structure
consisting
two
ions
bridged
four
acetate
molecules
on
both
axial
sites,
which
suggested
(i)
the
improved
solubility
ion
(ii)
enhanced
nucleophilicity
for
activation
phenylsilane.
1H
NMR
spectra
benzene-d6
solutions
containing
Cu(OAc)2,
2-(methylamino)pyridine,
showed
singlet
signal
at
2.62
ppm,
assigned
catalytically
active
Cu−H
species,
this
disappeared
upon
exposure
CO2.
formamide
synthesized
from
via
copper-catalyzed
hydrosilylation
under
conditions
directly
subjected
Grignard
reactions
in
THF
one-pot
synthesis
aldehydes
or
alcohols.
On
other
hand,
silyl
formates
prepared
using
tetrabutylammonium
(TBAA)
as
an
organocatalyst
were
also
found
be
good
precursors
As
service
our
authors
readers,
journal
provides
supporting
information
supplied
authors.
Such
materials
are
peer
reviewed
may
re-organized
online
delivery,
but
not
copy-edited
typeset.
Technical
support
issues
arising
(other
than
missing
files)
should
addressed
Please
note:
publisher
is
responsible
content
functionality
any
Any
queries
content)
directed
corresponding
author
article.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(22), P. 14935 - 14941
Published: May 9, 2024
The
catalytic
reactions
of
indoles
with
CO2
and
phenylsilane
afforded
indolo[3,2-b]carbazoles,
where
the
fused
benzene
ring
was
constructed
by
forming
two
C–H
bonds
four
C–C
molecules
via
deoxygenative
conversions.
Nine-membered
cyclophanes
made
up
three
were
also
obtained,
cyclophane
framework
six
bonds.
These
multicomponent
cascade
giving
completely
different
carbocycles
switched
simply
choosing
solvent,
acetonitrile
or
ethyl
acetate.
Molecules,
Journal Year:
2023,
Volume and Issue:
28(3), P. 1340 - 1340
Published: Jan. 31, 2023
The
development
and
application
of
new
organoboron
reagents
as
Lewis
acids
in
synthesis
metal-free
catalysis
have
dramatically
expanded
over
the
past
20
years.
In
this
context,
we
will
show
recent
uses
simple
relatively
weak
acid
BPh3—discovered
100
years
ago—as
a
catalyst
for
various
organic
transformations.
first
part
highlight
catalytic
applications
polymer
such
copolymerization
epoxides
with
CO2,
isocyanate,
anhydrides
to
polycarbonate
copolymers
controlled
diblock
well
alternating
polyurethanes.
This
is
followed
by
discussion
BPh3
component
frustrated
pair
(FLP)
mediated
cleavage
hydrogen
hydrogenation
catalysis.
addition,
BPh3-catalyzed
reductive
N-methylations
C-methylations
CO2
silane
value-added
products
be
covered
along
cycloadditions
insertion
reactions.
Collectively,
mini-review
showcases
underexplored
potential
commercially
available
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(9), P. 1370 - 1374
Published: Feb. 24, 2023
Catalytic
CO2
reduction
with
phenylsilane
under
solvent-free
conditions
was
linked
the
one-pot
synthesis
of
3,4-dihydropyrans
from
β-dicarbonyl
compounds
and
styrenes.
The
includes
three
processes:
(1)
bis(silyl)acetal
formation
a
domino
reaction
(2)
Knoevenagel
condensation
(3)
inverse-electron-demand
oxa-Diels-Alder
reaction.
first
process
catalyzed
by
pentanuclear
ZnII
complex
(0.07
mol
%)
to
generate
bis(silyl)acetals,
which
were
hydrolyzed
into
formaldehyde
be
used
in
second
step.
Materials,
Journal Year:
2023,
Volume and Issue:
16(23), P. 7309 - 7309
Published: Nov. 24, 2023
The
use
of
fossil
fuels
leads
to
significant
CO2
emissions,
thus
highlighting
the
importance
for
investigating
utilization
generating
high-value
chemical
products
toward
achieving
dual-carbon
goal.
can
be
efficiently
used
in
synthesizing
valuable
organic
compounds
through
C-C,
C-O,
C-H,
and
C-N
bond
construction,
with
reduction
technologies
effectively
converting
carbon
sources.
Therefore,
research
developing
environmentally
friendly
catalysts
efficient
renewable
conversion
holds
great
importance.
New
materials
catalytic
include
zeolites,
activated
carbon,
graphene,
metal-organic
frameworks
(MOFs),
covalent
(COFs),
ionic
liquids,
semiconducting
photocatalysts,
single-atom
(SACs),
dendritic
mesoporous
silica
nanoparticles
(DMSNs).
proper
these
aid
quest
reduce
emissions
mitigate
climate
change.
This
Review
focuses
on
liquids
(ILs),
(DMSNs),
carbene-metal
systems
conversion.
potential
new
catalyzing
is
examined
by
analyzing
various
common
sequestration
methods,
ultimately
providing
possible
directions
effective
solutions
environmental
pollution
problems.
On
basis
high
reaction
rate
treatment
efficiency
catalyst
CO2,
simpler
more
economical
synthesis
method
itself
wider
application
prospects.
Chemistry - An Asian Journal,
Journal Year:
2024,
Volume and Issue:
19(22)
Published: Aug. 17, 2024
Abstract
The
growing
emphasis
on
sustainable
chemistry
has
driven
research
into
utilizing
carbon
dioxide
(CO
2
)
as
a
nontoxic,
abundant,
and
cost‐effective
C1
building
block.
CO
offers
promising
avenue
for
direct
conversion
valuable
chemicals
ranging
from
fuels
to
pharmaceuticals.
This
review
focuses
the
utilization
of
reductive
N
‐formylation/
‐methylation
reactions
various
amines,
providing
advantages
over
conventional
methods
involving
toxic
other
methylating
reagents.
approach
employs
readily
available
reductants
such
silane,
borane
reagents,
hydrogen
(H
.
discussion
encompasses
recent
developments
in
transition
metal
organocatalyst
systems
these
reactions,
highlighting
mechanistic
interpretations
factors
influencing
product
selectivity.
Organic Chemistry Frontiers,
Journal Year:
2022,
Volume and Issue:
10(2), P. 375 - 381
Published: Nov. 21, 2022
A
polystyrene-supported
N-heterocyclic
organocatalyst
is
shown
to
be
a
versatile
system
for
the
N
-formylation
of
amines
using
carbon
dioxide
and
silanes,
heterogeneous
catalyst
can
potentially
applied
under
continuous
flow.
