Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 12, 2024
Enamides
have
emerged
as
robust
alternatives
for
enamines,
exhibiting
versatile
reactivity
further
synthetic
modifications,
including
nucleophilic
addition,
cycloaddition,
and
asymmetric
hydrogenation.
While
transition-metal-catalyzed
cross-coupling
of
alkenyl
(pseudo)halides
with
amides
has
been
widely
employed
to
construct
this
valuable
scaffold,
it
suffers
from
some
limitations,
such
the
need
transition-metal
catalysts
preparative
synthesis
(pseudo)halides.
In
study,
we
report
a
mild
convenient
stereoretentive
decarboxylative
amidation
α,β-unsaturated
carboxylic
acids
easily
procurable
1,4,2-dioxazol-5-ones,
providing
practical
route
enamides.
Density
functional
theory
(DFT)
calculations
revealed
plausible
reaction
mechanism,
which
involves
addition
carboxylate
onto
dioxazolone,
followed
by
sequential
concerted
rearrangements.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(20)
Published: March 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.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(20)
Published: March 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.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 12, 2024
Enamides
have
emerged
as
robust
alternatives
for
enamines,
exhibiting
versatile
reactivity
further
synthetic
modifications,
including
nucleophilic
addition,
cycloaddition,
and
asymmetric
hydrogenation.
While
transition-metal-catalyzed
cross-coupling
of
alkenyl
(pseudo)halides
with
amides
has
been
widely
employed
to
construct
this
valuable
scaffold,
it
suffers
from
some
limitations,
such
the
need
transition-metal
catalysts
preparative
synthesis
(pseudo)halides.
In
study,
we
report
a
mild
convenient
stereoretentive
decarboxylative
amidation
α,β-unsaturated
carboxylic
acids
easily
procurable
1,4,2-dioxazol-5-ones,
providing
practical
route
enamides.
Density
functional
theory
(DFT)
calculations
revealed
plausible
reaction
mechanism,
which
involves
addition
carboxylate
onto
dioxazolone,
followed
by
sequential
concerted
rearrangements.
