Organic Letters,
Год журнала:
2024,
Номер
26(44), С. 9519 - 9524
Опубликована: Окт. 25, 2024
We
report
a
dual
Ni/photoredox-catalyzed
cross-coupling
method
for
propargyl
carbonates
and
nonactivated
alkyl
bromides,
facilitating
the
synthesis
of
variety
substituted
allenes
under
mild
practical
conditions.
Mechanistically,
reaction
integrates
Ni-catalyzed
activation
electrophile
via
SN2′
oxidative
addition
at
Ni(I)
with
silyl
radical-induced
halide
through
halogen-atom
transfer.
This
methodology
provides
gentle
approach
introducing
allenyl
groups
into
complex
halogenated
aliphatic
molecules,
offering
further
opportunities
derivatization.
Pure and Applied Chemistry,
Год журнала:
2024,
Номер
96(3), С. 437 - 446
Опубликована: Март 1, 2024
Abstract
Disproportionation
and
comproportionation
reactions
have
become
routinely
proposed
events
in
modern
synthetic
endevours
that
use
nickel
catalysts.
This
new
found
appreciation
from
practitioners
the
field
for
these
electron
transfer
has
largely
stemmed
our
improved
understanding
of
catalytic
reactions.
These
studies
shown
evidence
ability
complexes
to
occupy
odd
even
oxidation
states
which
are
critical
dictating
reactivity.
Comproportionation
disproportionation
shuttle
between
essential
formation
either
on-cycle
or
off-cycle
species.
review
will
cover
fundamental
reactions,
provide
information
about
their
role
catalysis.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(28)
Опубликована: Апрель 25, 2024
Abstract
Aqueous
soluble
and
stable
Cu(I)
molecular
catalysts
featuring
a
catenane
ligand
composed
of
two
dicationic,
mutually
repelling
but
mechanically
interlocked
macrocycles
are
reported.
The
interlocking
not
only
fine‐tunes
the
coordination
sphere
kinetically
stabilizes
against
air
oxidation
disproportionation,
also
buries
hydrophobic
portions
ligands
prevents
their
dissociation
which
necessary
for
good
water
solubility
sustained
activity.
These
complexes
can
catalyze
oxidative
C−C
coupling
indoles
tetrahydroisoquinolines
in
water,
using
H
2
O
as
green
oxidant
with
substrate
scope.
successful
use
exploiting
aqueous
catalysis
thus
highlights
many
unexplored
potential
mechanical
bond
design
element
exploring
transition
metal
under
challenging
conditions.
Abstract
Numerous
reports
invoke
CuIII–F
intermediates
engaging
in
oxidative
cross-couplings
mediated
by
low/mid-valent
copper
and
formal
sources
of
‘F+’
oxidants.
These
elusive
typically
instable
CuIII
fluorides
have
been
rarely
characterized
or
spectroscopically
identified,
making
their
existence
participation
within
catalytic
cycles
somehow
questionable.
We
authenticated
a
stable
organocopper(III)
fluoride
that
undergoes
Csp–CF3
bond
formation
upon
addition
silyl-capped
alkynes
following
2
e–
CuIII/CuI
redox
shuttle.
This
finding
strongly
supports
the
intermediacy
C–C
coupling.
review
herein
state
art
about
well-defined
enabling
cross-coupling
reactions.
1
Introduction
Brief
History
Coupling-Competent
Fluorides
3
Design
an
Isolable
–
yet
Reactive
Organocopper(III)
Fluoride
4
Alkyne
Trifluoromethylation:
Scope
Mechanism
5
Extension
to
Aryl–CF3
C–Heteroatom
Couplings
6
Summary
Outlook
Organic Letters,
Год журнала:
2024,
Номер
26(44), С. 9519 - 9524
Опубликована: Окт. 25, 2024
We
report
a
dual
Ni/photoredox-catalyzed
cross-coupling
method
for
propargyl
carbonates
and
nonactivated
alkyl
bromides,
facilitating
the
synthesis
of
variety
substituted
allenes
under
mild
practical
conditions.
Mechanistically,
reaction
integrates
Ni-catalyzed
activation
electrophile
via
SN2′
oxidative
addition
at
Ni(I)
with
silyl
radical-induced
halide
through
halogen-atom
transfer.
This
methodology
provides
gentle
approach
introducing
allenyl
groups
into
complex
halogenated
aliphatic
molecules,
offering
further
opportunities
derivatization.
