In
this
work,
the
annulation
of
acyl
nitrene
with
alkynes
is
reported
under
photoredox/iron
dual-catalysis
for
synthesis
a
series
isoquninalin-2-ones.
The
reaction
featured
high
regioselectivity
and
good
generality.
particular,
resulting
isoquinalin-2-ones
could
be
structurally
elaborated
into
several
biologically
interesting
scaffolds.
Mechanism
investigation
suggests
that
was
ascribed
to
formal
[4
+
2]
cyclization.
It
believed
represents
an
initial
example
preparing
isoquinolin-1-ones
from
ferric
peroxyl-catalyzed
insertion.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(43), С. 29496 - 29502
Опубликована: Окт. 21, 2024
Removing
the
nitrogen
atom
from
secondary
amines
while
simultaneously
linking
remaining
fragments
is
a
powerful
form
of
late-stage
skeletal
editing.
Here,
we
report
its
use
for
deletion
dibenzylammonium
template
used
to
assemble
crown
ether
rotaxanes.
The
reaction
uses
an
anomeric
amide
that
activates
generate
carbon-carbon
bond
replaces
amine
nitrogen.
Despite
potential
dethreading
intermediate
diradical
pair,
was
successfully
deleted
series
rotaxane
axles
as
long
macrocycle
could
access
coconformations
did
not
inhibit
group.
skeletally
edited
interlocked
molecules
were
obtained
directly
parent
ether-dibenzylammonium
rotaxanes
in
modest
yields
(23-36%)
and
characterized
by
NMR
spectroscopy,
mass
spectrometry,
X-ray
crystallography.
One
shows
network
weak
CH···O
hydrogen
bonds
between
benzylic
methylene
groups
axle
solid
state,
place
ether-ammonium
binding
motif
parent,
unedited,
rotaxane.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Ноя. 24, 2024
Abstract
While
selective
defunctionalizations
are
valuable
in
organic
synthesis,
hydrodeamination
of
primary
amines
poses
challenges.
Deuterodeamination,
analogous
to
hydrodeamination,
presents
even
greater
difficulties
due
its
frequently
slower
deuteration
rate,
interference
by
hydrogenation
and
constraints
deuterated
sources.
This
study
introduces
a
reliable,
robust,
scalable
hydro-
deuterodeamination
method
capable
handling
various
amines.
Defined
mild
reaction
conditions,
rapid
completion,
simplified
purification
facilitated
water-soluble
byproducts,
the
leverages
deuterium
oxide
as
source
employs
commercialized
O-diphenylphosphinylhydroxylamine
for
deamination.
Applied
diverse
range
biologically
active
molecules,
it
has
consistently
achieved
high
yields
efficient
incorporation.
By
synergizing
with
site-selective
C–H
functionalization
aliphatic
amines,
our
reveals
synthetic
strategies
utilizing
nitrogen
atom
traceless
directing
group,
encompassing
deaminative
alkylation,
1,1-deuteroalkylation,
1,1-dialkylation,
1,1,1-deuterodialkylation,
arylation,
1,3-deuteroarylation.
Emphasizing
this
innovation,
processes
degree-controlled
have
been
developed.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 21, 2024
Skeletal
editing
is
an
important
approach
for
the
modification
and
diversification
of
biologically
active
molecules.
The
utilization
nitrogen
deletion
strategies
in
skeletal
has
recently
emerged
as
a
new
method
compound
modification.
Here,
we
report
unexpected
isoindolines.
Contrary
to
anticipated
outcome
cyclobutane
formation
via
intramolecular
radical
couplings,
isoindoline
triggers
Diels–Alder
cycloaddition
facilitated
by
situ
ortho-xylylene
yield
tetraline.
Inspired
this
reaction,
developed
strategy
synthesizing
substituted
tetralins,
employing
isoindoline,
reagent
(anomeric
amide),
dienophiles.
This
methodology
demonstrates
pathway
tetralin
synthesis
In
this
work,
the
annulation
of
acyl
nitrene
with
alkynes
is
reported
under
photoredox/iron
dual-catalysis
for
synthesis
a
series
isoquninalin-2-ones.
The
reaction
featured
high
regioselectivity
and
good
generality.
particular,
resulting
isoquinalin-2-ones
could
be
structurally
elaborated
into
several
biologically
interesting
scaffolds.
Mechanism
investigation
suggests
that
was
ascribed
to
formal
[4
+
2]
cyclization.
It
believed
represents
an
initial
example
preparing
isoquinolin-1-ones
from
ferric
peroxyl-catalyzed
insertion.
