Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(33)
Опубликована: Июнь 11, 2022
Strained
rings
are
increasingly
important
for
the
design
of
pharmaceutical
candidates,
but
cross-coupling
strained
remains
challenging.
An
attractive,
underdeveloped,
approach
to
diverse
functionalized
carbocyclic
and
heterocyclic
frameworks
containing
all-carbon
quaternary
centers
is
coupling
abundant
strained-ring
carboxylic
acids
with
aryl
halides.
Herein
we
disclose
development
a
nickel-catalyzed
cross-electrophile
that
couples
variety
ring
N-hydroxyphthalimide
(NHP)
esters,
derived
from
acid
in
one
step,
various
heteroaryl
halides
under
reductive
conditions.
The
chemistry
enabled
by
discovery
methods
control
NHP
ester
reactivity,
tuning
solvent
or
using
modified
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(11), С. 6270 - 6279
Опубликована: Март 7, 2023
An
electrochemically
driven
nickel-catalyzed
enantioselective
reductive
cross-coupling
of
aryl
aziridines
with
alkenyl
bromides
has
been
developed,
affording
enantioenriched
β-aryl
homoallylic
amines
excellent
E-selectivity.
This
electroreductive
strategy
proceeds
in
the
absence
heterogeneous
metal
reductants
and
sacrificial
anodes
by
employing
constant
current
electrolysis
an
undivided
cell
triethylamine
as
a
terminal
reductant.
The
reaction
features
mild
conditions,
remarkable
stereocontrol,
broad
substrate
scope,
functional
group
compatibility,
which
was
illustrated
late-stage
functionalization
bioactive
molecules.
Mechanistic
studies
indicate
that
this
transformation
conforms
stereoconvergent
mechanism
aziridine
is
activated
through
nucleophilic
halide
ring-opening
process.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(45)
Опубликована: Июнь 16, 2023
Abstract
Electrochemistry
utilizes
electrons
as
a
potent,
controllable,
and
traceless
alternative
to
chemical
oxidants
or
reductants,
typically
offers
more
sustainable
option
for
achieving
selective
organic
synthesis.
Recently,
the
merger
of
electrochemistry
with
readily
available
electrophiles
has
been
recognized
viable
increasingly
popular
methodology
efficiently
constructing
challenging
C−C
C‐heteroatom
bonds
in
manner
complex
molecules.
In
this
mini‐review,
we
have
systematically
summarized
most
recent
advances
electroreductive
cross‐electrophile
coupling
(eXEC)
reactions
during
last
decade.
Our
focus
on
electrophiles,
including
aryl
alkyl
(pseudo)halides,
well
small
molecules
such
CO
2
,
SO
D
O.
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:
2021,
Номер
143(25), С. 9332 - 9337
Опубликована: Июнь 15, 2021
Here
we
report
the
use
of
pulse
radiolysis
and
spectroelectrochemistry
to
generate
low-valent
nickel
intermediates
relevant
synthetically
important
Ni-catalyzed
cross-coupling
reactions
interrogate
their
reactivities
toward
comproportionation
oxidative
addition
processes.
Pulse
provided
a
direct
means
singly
reduced
[(dtbbpy)NiBr],
enabling
identification
rapid
Ni(0)/Ni(II)
process
taking
place
under
electrolysis
conditions.
This
approach
also
permitted
measurement
Ni(I)
rates
with
electronically
differentiated
aryl
iodide
electrophiles
(kOA
=
1.3
×
104–2.4
105
M–1
s–1),
an
elementary
organometallic
step
often
proposed
in
nickel-catalyzed
reactions.
Together,
these
results
hold
implications
for
number
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
60(11), С. 6107 - 6116
Опубликована: Дек. 8, 2020
Reported
here
is
the
redox
neutral
electrochemical
C(sp2
)-C(sp3
)
cross-coupling
reaction
of
bench-stable
aryl
halides
or
β-bromostyrene
(electrophiles)
and
benzylic
trifluoroborates
(nucleophiles)
using
nonprecious,
NiCl2
⋅glyme/polypyridine
catalysts
in
an
undivided
cell
configuration
under
ambient
conditions.
The
broad
scope
good
yields
Ni-catalyzed
coupling
reactions
were
confirmed
by
50
examples
aryl/β-styrenyl
chloride/bromide
trifluoroborates.
Potential
applications
demonstrated
electrosynthesis
late-stage
functionalization
pharmaceuticals
natural
amino
acid
modification,
three
run
on
gram-scale
a
flow-cell
electrolyzer.
C-C
proceed
through
unconventional
radical
transmetalation
mechanism.
This
method
highly
productive
expected
to
find
wide-spread
organic
synthesis.
