Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(9), P. 1813 - 1818
Published: Feb. 22, 2024
Herein,
we
present
a
novel
Catellani-type
reaction
that
employed
aryl-thianthrenium
salts
as
aryl
substrates
to
trigger
the
subsequent
palladium/norbornene
cooperatively
catalyzed
progress.
This
strategy
can
achieve
site-selective
C–H
difunctionalization
of
compounds
without
directing
groups
or
known
initiating
reagent.
A
series
functionalized
syntheses
bioactive
molecules
further
demonstrated
potential
this
strategy.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(41)
Published: July 9, 2024
In
this
work,
we
describe
an
efficient
and
modular
method
for
enantiodivergent
accessing
P(V)-stereogenic
molecules
by
utilizing
the
catalytic
atroposelective
Catellani-type
C-H
arylation/desymmetric
intramolecular
N-arylation
cascade
reaction.
The
enantioselectivity
of
protocol
was
proved
to
be
tuned
polarity
solvent,
thus
providing
a
wide
range
both
chiral
enantiomers
in
moderate
good
yields
with
excellent
enantiomeric
excesses.
Noteworthy
is
that
strategy
developed
herein
represents
unprecedented
example
solvent-dictated
inversion
compounds.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(37), P. 25552 - 25561
Published: Sept. 5, 2024
The
synthesis
of
complex
polysubstituted
aromatic
molecules
from
simple
precursors
is
a
central
goal
in
organic
chemistry.
In
this
study,
we
developed
an
approach
for
the
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 18, 2024
A
fundamental
property
of
cross-coupling
reactions
is
regiospecificity,
meaning
that
the
site
bond
formation
determined
by
leaving
group's
location
on
electrophile.
Typically,
achieving
a
different
substitution
pattern
requires
synthesis
new,
corresponding
starting-material
isomer.
As
an
alternative,
we
proposed
development
variants
would
afford
access
to
multiple
structural
isomers
from
same
coupling
partners.
Here,
first
demonstrate
bulky
palladium
catalyst
can
facilitate
efficient,
reversible
transposition
aryl
halides
temporarily
forming
metal
aryne
species.
Despite
nearly
thermoneutral
equilibrium
governing
this
process,
combining
it
with
gradual
addition
suitable
nucleophile
results
in
dynamic
kinetic
resolution
isomeric
intermediates
and
high
yields
unconventional
product
isomers.
The
method
accommodates
range
oxygen-
nitrogen-centered
nucleophiles
tolerates
numerous
common
functional
groups.
Curtin–Hammett
scheme
supported
computational
experimental
data,
providing
general
mechanistic
framework
for
extending
migratory
concept.
Cell Reports Physical Science,
Journal Year:
2023,
Volume and Issue:
4(11), P. 101647 - 101647
Published: Oct. 19, 2023
In
the
past
two
decades,
palladium
and
norbornene
(Pd/NBE)
co-catalyzed
cyclization
has
become
an
important
method
for
synthesis
of
natural
products,
drugs,
other
materials.
Herein,
we
disclose
a
Pd/NBE
three-component
ipso
intermolecular
alkyne
insertion
reaction.
The
reaction
pathway
first
undergoes
C-H
amination,
which
results
in
substituents
on
both
ortho-sites
aryl
intermediate.
Its
huge
steric
hindrance
poses
challenge
subsequent
insertion.
Mechanistic
studies
through
density
functional
theory
calculations
reveal
that
aryl-norbornyl-palladacycle
intermediates
do
not
react
with
alkynes,
migration
is
rate-determining
step
cyclization.
addition,
determine
key
role
cesium
carbonate
process.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(17), P. 3631 - 3635
Published: June 26, 2024
Abstract
Herein,
we
describe
a
strategy
for
the
synthesis
of
polycyclic
aromatic
hydrocarbons
(PAHs)
from
readily
available
2‐iodostyrenes
and
o
‐halobenzoic
acids
through
ligand‐free
palladium‐catalyzed
cascade
vinyl
C−H
activation/decarboxylative
cyclization.
A
vinyl‐coordinated
five‐membered
palladacycle
was
proposed
as
key
intermediate
this
sequential
process.
Furthermore,
Heptagon‐embedded
compounds
can
be
smoothly
synthesized
by
employing
8‐bromo‐1‐naphthoic
acid
decarboxylative
insertion
unit.
