Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Aug. 8, 2024
Building
C(sp3)-rich
architectures
using
simple
and
readily
available
starting
materials
will
greatly
advance
modern
drug
discovery.
C(sp3)−H
C(sp3)−O
bonds
are
commonly
used
to
strategically
disassemble
construct
bioactive
compounds,
respectively.
However,
the
direct
cross
coupling
of
these
two
chemical
form
C(sp3)−C(sp3)
is
rarely
explored
in
existing
literature.
Conventional
methods
for
forming
via
radical-radical
pathways
often
suffer
from
poor
selectivity,
severely
limiting
their
practicality
synthetic
applications.
In
this
study,
we
present
a
single
electron
transfer
(SET)
strategy
that
enables
cleavage
amine
α-C
−
H
heterobenzylic
C
O
bonds.
Preliminary
mechanistic
studies
reveal
hydrogen
bond
interaction
between
substrates
phosphoric
acid
facilitates
cross-coupling
radicals
with
high
chemoselectivity.
This
methodology
provides
an
effective
approach
variety
aza-heterocyclic
unnatural
amino
acids
molecules.
Herein,
authors
report
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(46), P. 25293 - 25303
Published: Nov. 8, 2023
Catalytic
carboamination
of
alkenes
is
a
powerful
synthetic
tool
to
access
valuable
amine
scaffolds
from
abundant
and
readily
available
alkenes.
Although
number
approaches
have
been
developed
achieve
the
rapid
buildup
molecular
complexity
in
this
realm,
installation
diverse
carbon
nitrogen
functionalities
onto
unactivated
remains
underdeveloped.
Here
we
present
ligand
design
approach
enable
nickel-catalyzed
three-component
carboamidation
that
applicable
wide
range
alkenyl
derivatives
via
tandem
process
involving
alkyl
migratory
insertion
inner-sphere
metal-nitrenoid
transfer.
With
method,
various
can
be
installed
into
both
internal
terminal
alkenes,
leading
differentially
substituted
diamines
would
otherwise
difficult
access.
Mechanistic
investigations
reveal
tailored
Ni(cod)(BQiPr)
precatalyst
modulates
electronic
properties
presumed
π-alkene-nickel
intermediate
quinone
ligand,
enhanced
carbonickelation
efficiency
across
C═C
bond.
These
findings
establish
nickel's
ability
catalyze
multicomponent
with
high
exquisite
selectivity.
Organometallics,
Journal Year:
2024,
Volume and Issue:
43(16), P. 1662 - 1681
Published: April 17, 2024
C(sp3)–C(sp3)
bond
formation
is
gaining
more
prominence,
especially
with
a
growing
emphasis
on
building
three-dimensional
chemical
space
in
bioactive
molecules,
fine
chemicals,
and
agrichemicals.
Metallaphotoredox
catalysis
has
emerged
as
an
effective
strategy
for
designing
processes
using
diverse
C(sp3)
precursors
well
suited
1e–
radical
chemistry.
This
review
summarizes
the
latest
advancement
metallaphotoredox
catalysis,
addressing
long-standing
challenges
cross-coupling,
focus
classification
of
reactions
based
distinct
modes
activation
precursor
upon
entering
catalytic
cycle.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Aug. 8, 2024
Building
C(sp3)-rich
architectures
using
simple
and
readily
available
starting
materials
will
greatly
advance
modern
drug
discovery.
C(sp3)−H
C(sp3)−O
bonds
are
commonly
used
to
strategically
disassemble
construct
bioactive
compounds,
respectively.
However,
the
direct
cross
coupling
of
these
two
chemical
form
C(sp3)−C(sp3)
is
rarely
explored
in
existing
literature.
Conventional
methods
for
forming
via
radical-radical
pathways
often
suffer
from
poor
selectivity,
severely
limiting
their
practicality
synthetic
applications.
In
this
study,
we
present
a
single
electron
transfer
(SET)
strategy
that
enables
cleavage
amine
α-C
−
H
heterobenzylic
C
O
bonds.
Preliminary
mechanistic
studies
reveal
hydrogen
bond
interaction
between
substrates
phosphoric
acid
facilitates
cross-coupling
radicals
with
high
chemoselectivity.
This
methodology
provides
an
effective
approach
variety
aza-heterocyclic
unnatural
amino
acids
molecules.
Herein,
authors
report
