Angewandte Chemie,
Год журнала:
2023,
Номер
136(8)
Опубликована: Дек. 23, 2023
Abstract
IMes
(IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene)
and
IPr
(IPr=1,3‐
bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene)
represent
by
far
the
most
frequently
used
N‐heterocyclic
carbene
ligands
in
homogeneous
catalysis,
however,
despite
numerous
advantages,
these
are
limited
lack
of
steric
flexibility
catalytic
pockets.
We
report
a
new
class
unique
unsymmetrical
that
characterized
freely‐rotatable
N‐aromatic
wingtips
imidazol‐2‐ylidene
architecture.
The
combination
rotatable
N−CH
2
Ar
bond
with
conformationally‐fixed
N−Ar
linkage
results
highly
modular
ligand
topology,
entering
range
geometries
inaccessible
to
IPr.
These
reactive
Cu(I)‐catalyzed
β‐hydroboration,
an
archetypal
borylcupration
process
has
had
transformative
impact
on
synthesis
boron‐containing
compounds.
Cu(I)‐NHC
this
been
commercialized
collaboration
MilliporeSigma
enable
broad
access
synthetic
chemistry
community.
gradually
cover
%V
bur
ranging
from
37.3
%
52.7
%,
latter
representing
largest
described
for
analogue,
while
retaining
full
N‐wingtip.
Considering
novel
geometrical
space
we
anticipate
concept
will
opportunities
organic
synthesis,
drug
discovery
stabilization
metal
centers.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(2), С. 1722 - 1731
Опубликована: Янв. 4, 2024
Herein,
we
report
a
ligand-controlled
palladium-catalyzed
method
that
enables
the
synthesis
of
ynones
and
γ-butenolides
with
excellent
regioselectivity
from
same
set
readily
available
aryl
iodides,
acetylenes,
BrCF2CO2K.
In
this
reaction,
[PdII]═CF2
does
demonstrate
electrophilicity
can
generate
CO
when
reacting
H2O.
It
is
environmentally
friendly
safe
compared
to
traditional
methods,
current
protocol
us
afford
in
high
yields
functionality
tolerance.
Moreover,
esters
also
be
obtained
corresponding
phenols
alcohols
utilizing
strategy.
The
success
late-stage
functionalization
bioactive
compounds
further
illustrates
synthetic
utility
material
development
drug
discovery.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(11), С. 2382 - 2431
Опубликована: Апрель 12, 2024
Abstract
This
contribution
offers
a
comprehensive
overview
of
methods
for
forging
sp
C−Si
bonds.
Over
time,
alkynylsilanes
(silylacetylenes),
once
considered
mere
byproducts
hydrosilylation
processes,
have
become
essential
building
blocks
in
organic
synthesis.
literature
review
traces
the
evolution
their
synthesis,
from
traditional
methodologies
relying
on
organolithium
and
organomagnesium
compounds
to
more
advanced
cross‐coupling
reactions
involving
hydro‐
carbosilanes.
Focused
primarily
past
25
years
(2000–2024),
it
also
extensively
references
significant
historical
breakthroughs.
By
analyzing
synthetic
methodologies,
not
only
survey
current
state
knowledge
but
identifies
areas
improvement.
Furthermore,
emphasize
importance
1‐alkynylsilanes
(1‐silyl‐1‐alkynes),
selected
applications
these
are
highlighted,
confirming
potential
Advanced Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 2, 2025
Amide
and
alkene
moieties
are
frequently
found
in
natural
products
privileged
structures
pharmaceuticals
agrochemicals.
Moreover,
vinyl
sulfoxonium
ylide
can
be
converted
into
a
broad
range
of
high-value
compounds,
thus
they
have
been
widely
employed
organic
synthesis.
However,
the
synthesis
alkene-substituted
amide-sulfoxonium
ylides
via
intermolecular
hydrocarbonation
alkynes
remains
underexplored.
This
study
describes
development
high-throughput
approach
to
provide
diverse
functionalized
E-alkene
substituted
(hetero)amide-sulfoxonium
ylides.
The
reaction
occurs
under
mild
metal-free
conditions,
employing
as
highly
effective
nucleophiles,
which
participate
Michael
addition
reactions
with
various
alkynes,
such
esters,
thioesters,
ketones,
amides,
sulfones.
low-cost,
operationally
simple
has
substrate
scope,
high
functional
group
compatibility,
excellent
regio-
stereoselectivity,
making
it
suitable
for
transformation
structurally
complex
molecules.
Furthermore,
obtained
stabilized
directly
useful
valuable
1,5-dicarbonyl
thiabenzene
1-oxide
compounds.
Chemical Science,
Год журнала:
2024,
Номер
15(48), С. 20346 - 20354
Опубликована: Янв. 1, 2024
A
highly
site-selective
decarbonylative
[4
+
2]
cyclization
of
carboxylic
acids
with
terminal
alkynes
forming
naphthalenes
is
enabled
by
palladium
cluster
catalysis.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(17), С. 12808 - 12815
Опубликована: Авг. 17, 2023
A
palladium-catalyzed
decarbonylative
annulation
of
2-arylbenzoic
acids
with
internal
alkynes
via
C(sp2)-H
activation
has
been
developed.
series
phenanthrenes
were
produced
in
moderate
to
good
yield
functional
group
tolerance.
The
mechanism
study
indicated
that
the
should
be
rate-determining
step
during
reaction.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(8)
Опубликована: Янв. 18, 2024
Abstract
The
ortho
C−H
methylation
and
ipso
C−O
alkenylation
of
aryl
triflates
was
regio‐selectively
achieved
in
one
pot
by
palladium/norbornene
(NBE)
synergistic
catalysis.
This
work
provides
an
efficient
method
for
preparing
poly‐substituted
aromatics
with
(deuterated)
methyl
alkenyl
groups
from
the
readily
available
phenoxides.
Abstract
The
catalytic
activity
of
the
supported
bis(oxime
palladacycle)
catalyst
was
evaluated
in
acyl
Sonogashira
reaction.
reaction
conditions,
such
as
solvent,
base,
and
palladium
content,
were
screened
to
achieve
best
performance.
Tetrahydrofuran
(THF)
triethylamine
(Et
3
N)
temperature
110
°C
found
be
ideal
for
achieving
high
yields
desired
products.
Furthermore,
a
loading
only
0.22
mol%
sufficient
good
conversion.
Broad
ranges
aryl
acetylenes
benzoyl
chlorides
successfully
coupled
give
acetylenic
ketones.
appeared
proceed
efficiently
using
small
amount
catalyst.
magnetic
property
allowed
easy
separation
an
external
magnet.
stable
reused
multiple
runs
without
significant
deactivation.
After
seven
cycles,
maintained
over
90
%
its
initial
activity.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(47), С. 9372 - 9378
Опубликована: Янв. 1, 2023
A
direct
deoxyfluorination
of
carboxylic
acids
by
utilizing
inorganic
potassium
fluoride
(KF)
as
a
safe
and
inexpensive
source
has
been
developed.
Both
aryl
cinnamyl
could
be
efficiently
transformed
into
valuable
acyl
fluorides
in
moderate
to
high
yields
with
good
functional
group
tolerance.
scale-up
reaction
carried
out
smoothly
under
solvent-free
conditions,
which
further
demonstrated
the
practicality
this
organic
synthesis.
