Empowered
by
the
ubiquity
of
carbonyl
functional
groups
in
organic
compounds,
decarbonylative
functionalization
was
prevalent
construction
complex
molecules.
Under
this
context,
asymmetric
has
emerged
as
an
efficient
pathway
to
accessing
chiral
motifs.
However,
ablation
enantiomeric
control
a
conventional
2e
transition
metal–catalyzed
process
notable
because
harsh
conditions
(high
temperatures,
etc.)
that
are
usually
required.
To
address
challenge
and
use
readily
accessible
aldehyde
directly,
we
report
radical
azidation
cyanation.
Diverse
aldehydes
were
directly
used
alkyl
precursor,
engaging
subsequent
inner-sphere
or
outer-sphere
ligand
transfer
where
motifs
(CN
N
3
)
could
be
incorporated
excellent
site-
enantioselectivity.
Mild
conditions,
broad
scope,
regioselectivity
(driven
polarity-matching
strategy),
enantioselectivity
shown
for
both
transformations.
This
strategy
using
precursor
offered
powerful
reaction
manifold
transformations
construct
regio-
stereoselectively.
Current
metal-free
methods
for
the
synthesis
of
alkyl
(1,2-di)azides
mainly
rely
on
highly
reactive
hypervalent
iodine
reagents
and
electrochemical
methods,
which
require
specialized
devices.
Herein,
we
show
a
robust
Selectfluor-promoted
oxidative
azidation
method,
can
effectively
achieve
selective
C(sp3)-H
bonds
in
alkanes/methylarenes
diazidation
alkenes,
without
involving
any
metal
catalyst
additive.
The
utility
this
method
is
highlighted
by
broad
substrate
scope,
late-stage
functionalization,
gram-scale
synthesis.
Mechanistic
studies
indicate
that
reaction
proceeds
via
radical
process.
Empowered
by
the
ubiquity
of
carbonyl
functional
groups
in
organic
compounds,
decarbonylative
functionalization
was
prevalent
construction
complex
molecules.
Under
this
context,
asymmetric
has
emerged
as
an
efficient
pathway
to
accessing
chiral
motifs.
However,
ablation
enantiomeric
control
a
conventional
2e
transition
metal–catalyzed
process
notable
because
harsh
conditions
(high
temperatures,
etc.)
that
are
usually
required.
To
address
challenge
and
use
readily
accessible
aldehyde
directly,
we
report
radical
azidation
cyanation.
Diverse
aldehydes
were
directly
used
alkyl
precursor,
engaging
subsequent
inner-sphere
or
outer-sphere
ligand
transfer
where
motifs
(CN
N
3
)
could
be
incorporated
excellent
site-
enantioselectivity.
Mild
conditions,
broad
scope,
regioselectivity
(driven
polarity-matching
strategy),
enantioselectivity
shown
for
both
transformations.
This
strategy
using
precursor
offered
powerful
reaction
manifold
transformations
construct
regio-
stereoselectively.
