Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(17), P. 3524 - 3541
Published: July 3, 2024
Abstract
The
radical
difunctionalization
of
unsaturated
hydrocarbons
serves
as
an
efficient
means
to
rapidly
construct
molecular
skeletons
and
synthesize‐highly
valuable
compounds.
In
this
transformational
process,
diverse
positions
within
are
sequentially
functionalized
by
a
single
precursor
reagent,
thereby
achieving
highly
selective
transformations
that
promote
atom
economy.
Furthermore,
approach
minimizes
the
generation
numerous
byproducts
stemming
from
cross‐coupling
reactions
between
reactants,
owing
reduction
number
participating
components.
Therefore,
review
provides
in‐depth
analysis
utilizing
functional
reagent
in
recent
decades.
discussion
is
based
on
eight
different
classes
(carbon‐,
nitrogen‐,
phosphine‐,
oxygen‐,
sulfur‐,
selenium‐,
tellurium‐,
chlorine‐centered
radicals),
emphasizing
mechanism
specific
difunctionalization.
It
also
analyzes
detail
regulation
key
factors
such
regional
selectivity,
unique
insights
into
reaction
transformations.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 6, 2025
A
water-controlled
geminal
phosphinoylation
of
enaminones
with
H-phosphine
oxides
has
been
established
through
AlCl3-mediated
C-N
bond
cleavage
in
this
work,
which
provides
a
novel
strategy
for
accessing
various
hydroxy
and
diphosphinoyl
products
3a
4a
high
yields.
The
transformation
features
excellent
functional
group
tolerance,
operational
simplicity,
atom
economy,
is
amenable
complex
molecule
skeletons.
Preliminary
mechanism
studies
suggest
the
conversion
from
to
involve
elimination
hydroxyl
group,
water
temperature
plays
critical
role
influencing
reaction
pathway
product
selectivity.
This
research
significant
value
functionalization
enaminones.
Organometallics,
Journal Year:
2024,
Volume and Issue:
43(10), P. 1095 - 1109
Published: April 24, 2024
The
synthesis
of
ethane-1,2-diyl-bis(diarylphosphane
oxides)
and
-phosphanes,
containing
bulky
ortho-substituted
P-bound
aryl
groups,
poses
severe
challenges,
such
as
drastic
reaction
conditions
low
yields.
A
potassium
base-mediated
hydrophosphorylation
phenylacetylene
with
dimesitylphosphane
oxide
(Mes2P(O)H)
yields
an
E/Z
mixture
alkenyl-dimesitylphosphane
oxide.
mesityl
group
hampers
the
addition
a
second
diarylphosphane
Contrary
to
this
expected
phosphane
across
alkyne
yielding
alkenylphosphane
oxide,
trimethylsilyl
acetylene
Mes2P(O)H
ethane-1,2-diyl-bis(dimesitylphosphane
oxide)
(2b);
surprisingly,
TMS
is
substituted
by
hydrogen
atom
via
rather
complex
mechanism.
Excess
TMS-C≡CH
(5
equiv),
ethereal
solvents,
soft
alkali
metal
catalysts,
large
catalyst
loadings
30
mol
%
are
highly
beneficial.
Furthermore,
at
least
one
ortho-position
must
be
alkylated,
whereas
very
groups
pose
no
obstacle.
Di(n-alkyl)phosphane
oxides
diphenylphosphane
do
not
show
described
conversion
but
react
completely
different.
Alternatively,
accessible
metathetical
approach
calcium
acetylide
CaC2
in
superbasic
solvent.
Reduction
these
(2)
phosphanes
(3)
offers
library
bidentate
ligands
for
coordination
chemistry
hard
(e.g.,
Y3+)
ions
Pd2+).
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 10, 2024
The
development
of
all
kinds
covalent
drugs
had
a
major
impact
on
the
improvement
human
health
system.
Covalent
binding
to
target
proteins
is
achieved
by
so-called
electrophilic
warheads,
which
are
incorporated
in
respective
drug
molecule.
In
last
decade,
specifically
acrylamides
emerged
as
attractive
warheads
design.
Herein,
straightforward
palladium-catalyzed
hydroaminocarbonylation
acetylene
has
been
developed,
allowing
modular
and
diverse
synthesis
bio-active
acrylamides.
This
general
protocol
features
high
atom
efficiency,
wide
functional
group
compatibility,
chemoselectivity
proceeds
additive
free
under
mild
reaction
conditions.
synthetic
utility
this
showcased
ibrutinib,
osimertinib,
other
compound
derivatives.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(40)
Published: July 10, 2024
Abstract
The
development
of
all
kinds
covalent
drugs
had
a
major
impact
on
the
improvement
human
health
system.
Covalent
binding
to
target
proteins
is
achieved
by
so‐called
electrophilic
warheads,
which
are
incorporated
in
respective
drug
molecule.
In
last
decade,
specifically
acrylamides
emerged
as
attractive
warheads
design.
Herein,
straightforward
palladium‐catalyzed
hydroaminocarbonylation
acetylene
has
been
developed,
allowing
modular
and
diverse
synthesis
bio‐active
acrylamides.
This
general
protocol
features
high
atom
efficiency,
wide
functional
group
compatibility,
chemoselectivity
proceeds
additive
free
under
mild
reaction
conditions.
synthetic
utility
this
showcased
ibrutinib,
osimertinib,
other
compound
derivatives.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 2, 2024
Herein,
a
Mn
catalytic
protocol
has
been
developed
for
the
cycloalkene
ring
expansion
synthesis
of
azaheterocycles,
allowing
broad-substrate-scope
access
to
pyridine
and
isoquinoline
derivatives.
The
initial
monoaddition
an
azidyl
radical
alkene
further
as-generated
C-radical
addition
O
