Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(24), С. 9527 - 9533
Опубликована: Март 19, 2020
Abstract
Self‐sustained
Ni
I/III
cycles
are
established
as
a
potentially
general
paradigm
in
photoredox
Ni‐catalyzed
carbon–heteroatom
cross‐coupling
reactions
through
strategy
that
allows
us
to
recapitulate
photoredox‐like
reactivity
the
absence
of
light
across
wide
range
substrates
amination,
etherification,
and
esterification
aryl
bromides,
latter
which
has
remained,
hitherto,
elusive
under
thermal
catalysis.
Moreover,
accessibility
is
especially
notable
because
previous
mechanistic
studies
on
this
transformation
conditions
have
unanimously
invoked
energy‐transfer‐mediated
pathways.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(4), С. 2081 - 2087
Опубликована: Янв. 23, 2023
Substantial
advances
in
enantioconvergent
C(sp3)-C(sp3)
bond
formations
have
been
made
with
nickel-catalyzed
cross-coupling
of
racemic
alkyl
electrophiles
organometallic
reagents
or
nickel-hydride-catalyzed
hydrocarbonation
alkenes.
Herein,
we
report
an
unprecedented
enantioselective
reductive
by
the
direct
utilization
two
different
halides
dual
nickel/photoredox
catalysis
system.
This
highly
selective
coupling
α-chloroboronates
and
unactivated
iodides
furnishes
chiral
secondary
boronic
esters,
which
serve
as
useful
important
intermediates
realm
organic
synthesis
enable
a
desirable
protocol
to
fast
construction
enantioenriched
complex
molecules.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Апрель 22, 2023
Here,
we
report
an
asymmetric
electrochemical
organonickel-catalyzed
reductive
cross-coupling
of
aryl
aziridines
with
iodides
in
undivided
cell,
affording
β-phenethylamines
good
to
excellent
enantioselectivity
broad
functional
group
tolerance.
The
combination
cyclic
voltammetry
analysis
the
catalyst
reduction
potential
as
well
electrode
study
provides
a
convenient
route
for
reaction
optimization.
Overall,
high
efficiency
this
method
is
credited
electroreduction-mediated
turnover
nickel
instead
metal
reductant-mediated
turnover.
Mechanistic
studies
suggest
radical
pathway
involved
ring
opening
aziridines.
statistical
serves
compare
different
design
requirements
photochemically
and
electrochemically
mediated
reactions
under
type
mechanistic
manifold.
Chemical Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 26, 2024
Cross-electrophile
coupling
(XEC),
defined
by
us
as
the
cross-coupling
of
two
different
σ-electrophiles
that
is
driven
catalyst
reduction,
has
seen
rapid
progression
in
recent
years.
As
such,
this
review
aims
to
summarize
field
from
its
beginnings
up
until
mid-2023
and
provide
comprehensive
coverage
on
synthetic
methods
current
state
mechanistic
understanding.
Chapters
are
split
type
bond
formed,
which
include
C(sp
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
142(12), С. 5884 - 5893
Опубликована: Фев. 29, 2020
Cross-electrophile
coupling
(XEC)
of
alkyl
and
aryl
halides
promoted
by
electrochemistry
represents
an
attractive
alternative
to
conventional
methods
that
require
stoichiometric
quantities
high-energy
reductants.
Most
importantly,
electroreduction
can
readily
exceed
the
reducing
potentials
chemical
reductants
activate
catalysts
with
improved
reactivities
selectivities
over
systems.
This
work
details
mechanistically-driven
development
electrochemical
methodology
for
XEC
utilizes
redox-active
shuttles
developed
energy-storage
community
protect
reactive
from
overreduction.
The
resulting
electrocatalytic
system
is
practical,
scalable,
broadly
applicable
reductive
a
wide
range
aryl,
heteroaryl,
or
vinyl
bromides
primary
secondary
bromides.
impact
overcharge
protection
as
strategy
electrosynthetic
methodologies
underscored
dramatic
differences
in
yields
reactions
added
redox
(generally
>80%)
those
without
<20%).
In
addition
excellent
substrates,
protected
overreduction
be
performed
at
high
currents
on
multigram
scales.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(24), С. 9527 - 9533
Опубликована: Март 19, 2020
Abstract
Self‐sustained
Ni
I/III
cycles
are
established
as
a
potentially
general
paradigm
in
photoredox
Ni‐catalyzed
carbon–heteroatom
cross‐coupling
reactions
through
strategy
that
allows
us
to
recapitulate
photoredox‐like
reactivity
the
absence
of
light
across
wide
range
substrates
amination,
etherification,
and
esterification
aryl
bromides,
latter
which
has
remained,
hitherto,
elusive
under
thermal
catalysis.
Moreover,
accessibility
is
especially
notable
because
previous
mechanistic
studies
on
this
transformation
conditions
have
unanimously
invoked
energy‐transfer‐mediated
pathways.
