Research Square (Research Square),
Journal Year:
2023,
Volume and Issue:
unknown
Published: July 5, 2023
Abstract
Given
the
high
demand
for
organophosphorus
compounds
(OPCs),
developments
of
sustainable
routes
toward
OPCs
synthesis
attract
much
attention.
Numerous
efforts
are
contributing
to
P
4
transformations
into
1
chemistry.
Nevertheless,
existing
methods
necessitate
energy-immense
multisteps
often
utilize
corrosive
and
dangerous
reagents
originating
from
/P
red
allotropes,
harmful
intermediates,
chemical
waste,
impeding
further
exploration
practical
applications.
Herein,
direct
efficient
transformation
inorganic
phosphates
[TBA][H
2
PO
]
is
demonstrated.
These
salts
were
activated
by
cost-efficient
oxalyl
chloride
at
20°C
in
5
minutes,
through
a
double
chlorination
OH
on
phosphorus
upon
elimination
CO
molecules,
followed
reducing
resultant
intermediate
with
trichlorosilane,
then
coupling
haloaryls
under
palladium-catalysis
provide
desired
OPCs.
Diverse
tolerance
various
functionalities
aryl
halides
achieved
potential
scale-up
industrial
applications,
eliminating
reliance
extortionate,
problematic
allotropes.
X-ray
diffraction
DFT
calculations
revealed
[TBA][PO
Cl
].
ChemistryEurope,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 7, 2025
Abstract
Compared
to
the
methods
that
rely
on
complex
and
structurally
unique
substrates
for
synthesis
of
heterocyclic
compounds
through
intra‐
intermolecular
cyclization,
strategies
starting
from
simple
readily
available
substrates,
combined
with
finely
tuned
catalytic
system
achieve
different
chemoselectivity,
offer
significant
advantages
in
terms
efficiency,
cost‐effectiveness,
versatility.
Herein,
we
present
a
palladium‐catalyzed
carbonylation
strategy
enables
selective
efficient
isoquinoline‐1,3(2
H
,4
)‐dione
indanone
derivatives
via
distinct
reaction
pathways.
Notably,
chemoselectivity
was
not
determined
by
differences
reactivity
at
sites
but
instead
arises
generation
active
palladium
species
under
nearly
identical
conditions,
which
subsequently
react
same
site
lead
products.
Organic Chemistry Frontiers,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
A
palladium-catalyzed
chemoselective
decarboxylative
coupling
of
alkynyl
carboxylic
acids
with
halogenated
aryl
triflates
has
been
developed
for
the
efficient
synthesis
OTf-arylalkyne
scaffolds.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(23), P. 16609 - 16620
Published: Nov. 18, 2023
A
1,8-diazabicyclo[5.4.0]undec-7-ene-promoted
cascade
double-annulation
of
ortho-alkynyl
quinone
methide
(in
situ
generated
from
modular
propargylamine)
for
constructing
2-aryl-4-hydroxybenzo[c]chromen-6-ones
is
developed.
This
synthetic
strategy
offers
remarkable
operational
simplicity
as
it
allows
the
use
benchtop-grade
solvents
without
need
predrying
measures
and
inert
atmosphere
protection.
Additionally,
demonstrates
good
functional
group
compatibility.
The
photophysical
properties
these
compounds
were
also
examined,
revealing
bright
fluorescence
with
high
quantum
yields.
Abstract
This
study
describes
the
palladium‐catalyzed
chemoselective
amination
of
chloro(hetero)aryl
triflates
in
C−Cl
bond
for
first
time.
A
newly
designed
and
synthesized
alkyl‐pyrazole‐based
phosphine
ligand,
L26
(
BirdPhos
),
which
is
featured
with
pyrazole
ligand
core
cyclohexyl
group
at
C3
C5
positions,
was
key
to
success
this
reaction.
variety
coupled
aromatic,
aliphatic,
heterocyclic
amines
smoothly
afforded
corresponding
products
up
97%
yields
general
chemoselectivity
(>99%)
bond.
Drug
analogs
were
also
via
intermolecular
amination.
attempts
investigate
structure‐activity
relationship
new
class
through
experimental
density
functional
theory
(DFT)
calculations.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(22), P. 16262 - 16268
Published: Feb. 12, 2024
We
present
an
advancement
in
synthesizing
organophosphorus
compounds
via
chemoselective
phosphorylation
achieved
by
a
palladium
and
SelectPhos
ligand
system
(Pd/L1).
This
catalysis
exhibits
remarkable
chemoselectivity,
even
poly(pseudo)halide
substrates
overcoming
toxicity
substrate
scope
limitations.
The
catalytic
is
robust,
which
demonstrated
across
diverse
such
as
chloroaryl
bromoaryl
triflates.
Furthermore,
we
one-pot
sequential
strategy
combining
with
Suzuki–Miyaura
coupling,
providing
versatile
platform
for
the
efficient
synthesis
of
complex
compounds,
challenging
conventional
reactivity
paradigms.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
11(21)
Published: March 14, 2024
Abstract
A
series
of
new
pyrazole‐alkyl
phosphine
ligands
with
varying
cycloalkyl
ring
sizes
that
enable
additive‐free
regio‐
and
chemoselective
C─H
arylation
heterocycles
are
reported.
Excellent
α/β
selectivity
various
such
as
benzo[
b
]thiophene,
thiophene,
furan,
benzofuran,
thiazole
can
be
achieved
using
these
ligands,
along
excellent
chemoselectivity
C─Cl
over
C─OTf
chloroaryl
triflates.
Mechanistic
studies
supported
by
both
experimental
findings
density
functional
theory
calculations
indicate
the
pyrazole
optimal
allow
reaction
to
proceed
a
lower
energy
barrier
via
concerted
metalation–deprotonation
pathway.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(13), P. 9243 - 9254
Published: June 15, 2024
Chemoselective
amination
is
a
highly
desired
synthetic
methodology,
given
its
importance
as
possible
strategy
to
synthesize
various
drug
molecules
and
agrochemicals.
We,
herein,
disclose
chemoselective
Cu(II)-PTABS-promoted
of
pyrimidine
structural
feature
containing
different
halogen
atoms.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(47), P. 8429 - 8433
Published: Nov. 17, 2023
In
this
study,
a
novel
and
efficient
Pd-catalyzed
chemoselective
deuterodehalogenation
reaction
of
halogenated
aryl
triflates
was
developed
using
isopropanol-d8
as
the
deuterium
source.
This
afforded
an
unconventional
chemoselectivity
order
C-Br
>
C-Cl
C-OTf.
catalytic
system
successfully
applied
to
hydrodehalogenation
chloroaryl
triflates,
providing
excellent
over
