Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(18), P. 5016 - 5025
Published: Jan. 1, 2024
An
efficient
method
for
the
remote
heteroarylation
of
unactivated
C(sp
3
)–H
bonds
has
been
developed
involving
a
silyl
radical-mediated
relay
reaction.
B-Amino
acids
are
useful
building
blocks
of
bioactive
molecules,
including
peptidomimetics
and
pharmaceutical
compounds.
The
current
limited
accessibility
to
B-2,2-type
amino
which
bear
an
a-quaternary
center
has
their
use
in
chemical
synthesis
biological
investigations.
Disclosed
herein
is
the
development
a
new
N-heterocyclic
carbene/photocatalyzed
aminocarboxylation
olefins,
affording
B-2,2-amino
esters
with
high
regioselectivity.
generation
nitrogen-centered
radicals
derived
from
simple
imides
via
se-quence
deprotonation
single-electron
oxidation
allows
for
subsequent
addition
gem-disubstituted
olefins
regioselectively.
intermediate
tertiary
then
cross-couple
stabilized
azolium-based
radical
generated
situ
efficiently
construct
quaternary
centers.
Mechanistic
studies
Stern-Volmer
fluorescence
quenching
experiments
support
proposed
catalytic
cycle.
Journal of Synthetic Organic Chemistry Japan,
Journal Year:
2024,
Volume and Issue:
82(3), P. 222 - 233
Published: March 1, 2024
One
of
the
privileged
motifs
chiral
N-heterocyclic
carbene
(NHC)
catalyst
is
an
aminoindanol-derived
structure,
and
many
researchers
achieved
improvement
this
type
by
introducing
various
substitutions
at
triazolium
nitrogen,
which
located
proximal
site
reactive
carbene.
Recently,
we
found
that
introduction
substituents
benzene
ring
indane
moiety,
far
from
carbon,
could
efficiently
tune
catalytic
activity
NHC
catalysts
in
enantioselective
acylation
racemic
alcohols,
asymmetric
intramolecular
Stetter
reactions,
intermolecular
benzoin
condensation
benzaldehyde
derivatives.
Herein,
report
development
novel
high-performance
remote
substituent
effects.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(18), P. 5016 - 5025
Published: Jan. 1, 2024
An
efficient
method
for
the
remote
heteroarylation
of
unactivated
C(sp
3
)–H
bonds
has
been
developed
involving
a
silyl
radical-mediated
relay
reaction.