Angewandte Chemie,
Год журнала:
2023,
Номер
135(42)
Опубликована: Авг. 12, 2023
Abstract
An
unprecedented
Pd‐catalyzed
fluorinative
bifunctionalization
of
aziridines
and
azetidines
was
successfully
developed
via
regioselective
C−C
C−F
bond
cleavage
gem‐difluorocyclopropanes,
leading
to
various
β,β′‐bisfluorinated
amines
β,γ‐bisfluorinated
amines.
This
reaction
achieved
by
incorporating
a
2‐fluorinated
allyl
group
fluorine
atom
scissored
from
gem‐difluorocyclopropane
in
100
%
economy
for
the
first
time.
The
mechanistic
investigations
indicated
that
underwent
amine
attacking
palladium
complex
generate
η
2
‐coordinated
N‐allyl
aziridine
followed
fluoride
ligand
transfer
affording
final
β‐
γ‐fluorinated
Angewandte Chemie,
Год журнала:
2024,
Номер
136(20)
Опубликована: Март 19, 2024
Abstract
Herein,
multiple
types
of
chiral
Os(II)
complexes
have
been
designed
to
address
the
appealing
yet
challenging
asymmetric
C(sp
3
)−H
functionalization,
among
which
Os(II)/Salox
species
is
found
be
most
efficient
for
precise
stereocontrol
in
realizing
amidation.
As
exemplified
by
enantioenriched
pyrrolidinone
synthesis,
such
tailored
catalyst
efficiently
enables
an
intramolecular
site‐/enantioselective
amidation
γ‐position
dioxazolone
substrates,
benzyl,
propargyl
and
allyl
groups
bearing
various
substituted
forms
are
well
compatible,
affording
corresponding
γ‐lactam
products
with
good
er
values
(up
99
:
1)
diverse
functionality
(>35
examples).
The
unique
performance
advantage
developed
system
terms
catalytic
energy
profile
induction
has
further
clarified
integrated
experimental
computational
studies.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(15), С. 11003 - 11008
Опубликована: Июль 17, 2024
We
present
a
one-pot
reaction
that
offers
an
efficient
approach
to
synthesizing
tetrasubstituted
vinyl
sulfides
with
high
stereoselectivity.
This
method
involves
the
sequential
Wolff
rearrangement,
ylide
formation,
and
[1,4]-aryl
transfer
by
utilizing
aryl
alkyl
thiols
α-diazo
carbonyl
compounds
as
substrates.
Notably,
this
features
commercially
available
materials,
straightforward
operation,
atom
economy,
broad
substrate
scope.
Moreover,
primary
photophysical
properties
(aggregation-induced
emission
effect)
of
products
were
also
investigated,
which
might
be
useful
in
functional
materials
via
structural
modification.
Abstract
A
rhodium‐catalyzed
cascade
migration‐annulation
reaction
of
1‐sulfonyl‐1,2,3‐triazole
has
been
developed.
As
the
key
step,
1,3‐sulfinate
migration
α‐imino
rhodium
carbene
yielded
an
extended
zwitterion,
which
was
intramolecularly
trapped
by
aldehyde
group
furnishing
bridged
N,O
‐heterocyclic
1,6‐epoxybenzo[c]azocine
as
[5+2]
cyclization
product.
This
strategy
provides
more
flexibility
for
heterocycle
synthesis
and
medium‐sized
ring
construction,
especially
construction
polycycles
with
complex
skeletons.
Angewandte Chemie,
Год журнала:
2023,
Номер
135(42)
Опубликована: Авг. 12, 2023
Abstract
An
unprecedented
Pd‐catalyzed
fluorinative
bifunctionalization
of
aziridines
and
azetidines
was
successfully
developed
via
regioselective
C−C
C−F
bond
cleavage
gem‐difluorocyclopropanes,
leading
to
various
β,β′‐bisfluorinated
amines
β,γ‐bisfluorinated
amines.
This
reaction
achieved
by
incorporating
a
2‐fluorinated
allyl
group
fluorine
atom
scissored
from
gem‐difluorocyclopropane
in
100
%
economy
for
the
first
time.
The
mechanistic
investigations
indicated
that
underwent
amine
attacking
palladium
complex
generate
η
2
‐coordinated
N‐allyl
aziridine
followed
fluoride
ligand
transfer
affording
final
β‐
γ‐fluorinated
