Angewandte Chemie,
Год журнала:
2023,
Номер
135(51)
Опубликована: Ноя. 6, 2023
Abstract
Attaching
a
nitrene
precursor
to
an
intramolecular
nucleophile
allows
for
catalytic
asymmetric
oxyamination
of
alkenes
in
which
the
adds
endocyclic
position
and
amine
exocyclic
fashion.
Using
chiral‐at‐ruthenium
catalysts,
chiral
γ‐aminomethyl‐γ‐lactones
containing
quaternary
carbon
γ‐position
are
provided
high
yields
(up
99
%)
with
excellent
enantioselectivities
%
ee
).
DFT
calculations
support
possibility
both
singlet
(concerted
alkene)
triplet
pathway
(stepwise
oxyamination)
formation
predominant
stereoisomer.
γ‐Aminomethyl‐γ‐lactones
versatile
building
blocks
can
be
converted
other
heterocycles
such
as
δ‐lactams,
2‐oxazolidinones,
tetrahydrofurans.
Organic Process Research & Development,
Год журнала:
2023,
Номер
28(5), С. 1567 - 1575
Опубликована: Сен. 11, 2023
A
new
and
highly
efficient
continuous
flow
process
is
presented
for
the
synthesis
of
aziridines
via
thermal
Baldwin
rearrangement.
The
was
initially
explored
using
traditional
batch
techniques
but
suffered
from
moderate
yields,
long
reaction
times,
diastereoselectivities.
Here
we
demonstrate
that
can
be
greatly
improved
upon
its
transfer
to
flow,
which
afforded
aziridine
targets
in
high
short
consistently
diastereoselectivities,
with
high-throughput
rendering
multigram
quantities
product
periods
time.
In
addition,
processing
extended
substrate
scope
including
several
examples
had
failed
mode,
thus
demonstrating
value
this
overlooked
entry
into
valuable
species.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(30)
Опубликована: Май 13, 2024
Abstract
N‐acyl
iminophosphoranes
have
shown
significant
potentials
in
various
areas.
This
paper
presents
two
electrochemical
strategies
for
the
successful
construction
of
a
series
substituted
using
activation
hydroxylamines
or
dioxazolones
to
generate
unprotected
amide
radicals
and
radical
anions.
The
simple
undivided
cell
with
inexpensive
electrode
setups
(graphite
felts,
carbon
rods,
copper
sheets)
provides
excellent
substrates
tolerance
under
mild
conditions.
also
has
good
scalability,
practicability
extensibility.
Furthermore,
synthetic
transformations
iminophosphorane
products
demonstrated
application
P=N
bond.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(15), С. 3346 - 3353
Опубликована: Июнь 5, 2024
Abstract
Synthesis
of
new
polysubstituted
furans
incorporating
reactive
phosphorus
ylides
or
N
‐acyliminophosphoranes
was
achieved
by
the
heterocyclization
flexible
α‐acyl
ketene
dithioacetals.
This
one‐pot
tandem
reaction
initiated
acyl‐directed
desulfurative
Sonogashira
coupling,
followed
1,6‐addition
phosphine
to
in
situ‐generated
enynone
and
subsequent
5‐
exo
‐
dig
cyclization,
as
well
phosphoranation.
The
selectivity
toward
two
products,
i.
e.
α‐phosphorus
vs.
α‐
‐acyliminophosphoranes‐substituted
furans,
determined
both
electron‐deficient
acetylenes
copper
salts.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(16), С. 3350 - 3354
Опубликована: Янв. 1, 2023
Herein,
we
report
the
generation
of
iminyl
radicals
through
photocatalytic
deoxygenation
oximes
with
trivalent
phosphine.
The
hydroimination
reaction
proceeded
via
β-scission
a
phosphoranyl
radical,
followed
by
5-exo-trig
cyclization
resulting
radical.
This
protocol
transforms
oximes,
including
alkyl
into
variety
pyrrolines
in
moderate
to
good
yields.
A
radical
clock
experiment
confirmed
formation
cyclic
and
supported
our
design.
Angewandte Chemie,
Год журнала:
2023,
Номер
135(51)
Опубликована: Ноя. 6, 2023
Abstract
Attaching
a
nitrene
precursor
to
an
intramolecular
nucleophile
allows
for
catalytic
asymmetric
oxyamination
of
alkenes
in
which
the
adds
endocyclic
position
and
amine
exocyclic
fashion.
Using
chiral‐at‐ruthenium
catalysts,
chiral
γ‐aminomethyl‐γ‐lactones
containing
quaternary
carbon
γ‐position
are
provided
high
yields
(up
99
%)
with
excellent
enantioselectivities
%
ee
).
DFT
calculations
support
possibility
both
singlet
(concerted
alkene)
triplet
pathway
(stepwise
oxyamination)
formation
predominant
stereoisomer.
γ‐Aminomethyl‐γ‐lactones
versatile
building
blocks
can
be
converted
other
heterocycles
such
as
δ‐lactams,
2‐oxazolidinones,
tetrahydrofurans.
