ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(21), P. 15858 - 15868
Published: Oct. 11, 2024
The
catalytic
hydrofunctionalization
of
alkenes
with
nucleophiles
via
the
generation
carbocationic
intermediates
has
been
extensively
studied
as
an
efficient
strategy
for
regioselective
installation
functional
groups
on
alkene
feedstocks.
However,
since
established
methods
are
confined
to
functionalization
position
where
is
originally
located,
it
highly
desirable
develop
a
broadly
applicable
platform
that
offers
alternative
regioselectivity
otherwise
challenging
achieve
existing
protocols.
Herein,
we
report
remote
method
enabled
by
electrooxidative
palladium
hydride
catalysis.
key
success
formation
carbocation
intermediate
through
mechanistic
pathway,
which
involves
chain-walking
process
followed
anodic
oxidation
organopalladium
species.
This
allows
terminal
and
internal
broad
range
oxygen,
carbon,
nitrogen,
fluoride
nucleophiles,
including
complex
drug-like
molecules.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(26)
Published: April 15, 2024
In
contrast
to
the
kinetically
favored
outward
isomerization-hydrocarbonylation
of
alkenes,
disfavored
inward
alkenes
remains
an
important
challenge.
Herein,
we
have
developed
a
novel
and
effective
palladium-catalyzed
isomerization-hydroaminocarbonylation
unactivated
aniline
hydrochlorides
for
formation
synthetically
valuable
α-aryl
carboxylic
amides
in
high
yields
site-selectivities.
The
efficiency
reaction
is
attributed
relay
catalysis
strategy,
which
Markovnikov-favored
[PdH]-P
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(29)
Published: April 29, 2024
Abstract
Cyclic
sulfones
have
demonstrated
important
applications
in
drug
discovery.
However,
the
catalytic
and
enantioselective
synthesis
of
chiral
cyclic
remains
challenging.
Herein,
we
develop
nickel‐catalyzed
regiodivergent
hydroalkylation
sulfolenes
to
streamline
alkyl
sulfones.
The
method
has
broad
scope
high
functional
group
tolerance.
regioselectivity
can
be
controlled
by
ligands
only.
A
neutral
PYROX
ligand
favors
C3‐alkylation
whereas
an
anionic
BOX
C2‐alkylation.
This
control
is
kinetic
origin
as
C2‐bound
Ni
intermediates
are
always
thermodynamically
more
stable.
Reactivity
study
a
wide
range
relevant
reveal
I
/Ni
III
cycle
with
II
−H
species
resting
state.
regio‐
enantio‐determining
step
insertion
this
into
2‐sulfolene.
work
provides
efficient
for
class
organic
compounds
enhances
mechanistic
understanding
Ni‐catalyzed
stereoselective
hydroalkylation.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(14), P. 5277 - 5283
Published: Jan. 1, 2024
Chemodivergent
construction
of
structurally
distinct
heterocycles
from
the
same
precursors
by
adjusting
specific
reaction
parameters
is
an
emergent
area
organic
synthesis;
yet,
understanding
processes
that
underpin
divergence
lacking,
preventing
development
new
synthetic
methods
systematically
harnessing
key
mechanistic
effects.
We
describe
herein
cesium
carbonate-promoted
oxadiaza
excision
cross-coupling
reactions
β-ketoesters
with
1,2,3-triazine
1-oxides
form
pyridones
in
good
to
high
yields,
instead
sole
formation
pyridines
when
performed
presence
other
alkali
metal
carbonates
or
bases.
The
can
be
further
extended
synthetically
challenging
pyridylpyridones.
A
computational
study
comparing
effect
and
sodium
ions
reveals
cesium-coordinated
species
changes
preference
attack
at
ketone
carbonyl
ester
carbon
due
ion-specific
transition
state
conformational
accommodation,
revealing
a
previously
unexplored
role
may
facilitate
chemodivergent
approaches
heterocyclic
systems.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(23)
Published: April 17, 2024
Abstract
This
paper
reports
the
construction
of
racemic
and
enantiopure
(D‐
L‐)
fluorene
fluorenone‐based
novel
unnatural
amino
acid
derivatives.
The
Pd(II)‐catalyzed
bidentate
directing
group‐aided
arylation
prochiral
β
‐C(sp
3
)‐H
bonds
in
racemic,
carboxamides
acids
with
iodofluorenes
was
reported.
examples
fluorenone
motifs
containing
comprising
norvaline,
leucine,
phenylalanine,
norleucine,
2‐aminooctanoic
derivatives
having
anti
‐stereochemistry
(with
good
enantiopurity)
accomplished.
bis
fluorenyl
alanine
scaffolds
motif‐containing
non‐
α
‐amino
(aminoalkanoic
acid)
also
Examples
removal
group
(8‐aminoquinoline)
phthalimide‐protecting
present
fluorenyl‐based
have
been
shown.
Accordingly,
motif‐based
esters
free
group‐containing
were
synthesized.
stereochemistry
major
(
)
diastereomers
obtained
via
ascertained
from
X‐ray
structure
a
representative
compound.
Fluorene‐
are
vital
skeletons
materials
medicinal
chemistry
research.
this
work
is
contribution
towards
enriching
library
scaffolds.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(26)
Published: April 15, 2024
Abstract
In
contrast
to
the
kinetically
favored
outward
isomerization‐hydrocarbonylation
of
alkenes,
disfavored
inward
alkenes
remains
an
important
challenge.
Herein,
we
have
developed
a
novel
and
effective
palladium‐catalyzed
isomerization‐hydroaminocarbonylation
unactivated
aniline
hydrochlorides
for
formation
synthetically
valuable
α‐aryl
carboxylic
amides
in
high
yields
site‐selectivities.
The
efficiency
reaction
is
attributed
relay
catalysis
strategy,
which
Markovnikov‐favored
[PdH]‐P
t
Bu
3
catalyst
responsible
isomerization,
while
[PdH]‐Ruphos
hydroaminocarbonylation
resulting
conjugated
aryl
alkenes.
exhibits
highly
functional
group
tolerance
provides
new
method
formal
carbonylation
remote
C(sp
)−H
bond.
