Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(42), С. 29177 - 29188
Опубликована: Окт. 12, 2024
Tertiary
alkylamines
are
privileged
structural
motifs
widely
present
in
natural
products,
pharmaceutical
agents,
and
bioactive
molecules,
their
efficient
synthesis
has
been
a
longstanding
goal
organic
chemistry.
The
functionalization
of
α-amino
radicals
derived
from
abundant
precursors
represents
an
emerging
approach
to
accessing
alkylamines,
but
application
this
strategy
obtain
tertiary
remains
challenging.
Here,
we
show
that
dual
photoredox/nickel
catalysis
enables
aminoalkylation
organohalides
(sp
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 28, 2025
Abstract
Motivated
by
the
inherent
benefits
of
synergistically
combining
electrochemical
methodologies
with
nickel
catalysis,
we
present
here
a
Ni-catalyzed
enantioselective
electroreductive
cross-coupling
benzyl
chlorides
aryl
halides,
yielding
chiral
1,1-diaryl
compounds
good
to
excellent
enantioselectivity.
This
catalytic
reaction
can
not
only
be
applied
chlorides/bromides,
which
are
challenging
access
other
means,
but
also
containing
silicon
groups.
Additionally,
absence
sacrificial
anode
lays
foundation
for
scalability.
The
combination
cyclic
voltammetry
analysis
electrode
potential
studies
suggests
that
Ni
I
species
activate
halides
via
oxidative
addition
and
alkyl
single
electron
transfer.
A
Ni/photoredox
dual-catalyzed
multicomponent
cross-electrophile
coupling
of
N-vinyl
amides
with
(hetero)aryl
halides
and
(2°,
3°)-alkyl
redox-active
esters
in
the
presence
cheap
reductant
Hantzsch
ester
is
reported
here.
This
reductive
protocol
provides
direct
access
to
various
synthetically
challenging
chiral
α-arylamides
good
yields
excellent
enantioselectivities
(up
99%
ee,
majority
exceeding
97%
ee),
which
can
be
further
derived
into
primary
secondary
amines.
Preliminary
experimental
studies
shed
light
on
potential
catalytic
pathways.
The Chemical Record,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 3, 2025
Abstract
Owing
to
their
wide
utilizations
in
synthesis
and
products
prevalence
numerous
natural
products,
pharmaceuticals
functional
materials,
the
alkene
difunctionalization
methods
for
selective
transformations
of
olefins
are
important
have
attracted
much
attention
form
synthetic
chemists.
Among
them,
electrochemical
reaction
is
particularly
promising
has
becoming
a
potent
sustainable
tool
alkenes
into
vicinal
difunctionalized
structures
organic
through
simultaneous
incorporation
two
groups.
Herein,
we
summarize
recent
progress
reactions
according
types
as
well
category
radicals
over
past
five
years.
By
selecting
remarkable
examples,
elaborately
discussed
substrate
scope
mechanisms
olefin
reaction.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 8, 2025
Comprehensive
Summary
Herein,
we
present
the
first
examples
of
asymmetric
reductive
1,4‐dicarbofunctionalization
1,3‐dienes
and
1,5‐dicarbofunctionalization
vinylcyclopropanes,
which
proceed
under
catalysis
a
chiral
nickel/bis‐imidazoline
complex
using
alkyl
halides
aryl
iodides
or
alkenyl
bromides
as
electrophilic
coupling
partners.
In
these
highly
enantioselective
transformations
operating
in
radical
relay
mechanism,
C(sp
3
)‐
2
)‐type
carbo‐moieties
are
respectively
installed
on
terminal
internal
position
with
newly
formed
olefinic
unit
high
E
‐selectivity.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(9), С. 6106 - 6116
Опубликована: Апрель 18, 2024
An
electrochemical
oxidative
cross-coupling
strategy
for
the
synthesis
of
N-sulfenylsulfoximines
from
sulfoximines
and
thiols
was
accomplished,
giving
diverse
in
moderate
to
good
yields.
Moreover,
this
can
be
extended
construct
N–P
bond
N-phosphinylated
sulfoximines.
With
electrons
as
reagents,
dehydrogenation
reaction
proceeds
smoothly
absence
traditional
redox
reagents.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(22), С. 4390 - 4419
Опубликована: Янв. 1, 2024
The
merger
of
organic
electrosynthesis
with
3d
transition-metal
catalysis
has
offered
huge
opportunities
for
modern
synthesis.
This
review
summarizes
the
key
advancements
in
this
direction
published
recent
two
years.
Radical-involved
arylative
cross-coupling
reactions
have
recently
emerged
as
an
attractive
strategy
to
access
valuable
aryl-substituted
motifs.
However,
there
still
exist
several
challenges
such
limited
scope
of
radi-cal
precursors/acceptors,
and
lack
general
asymmetric
catalytic
systems,
especially
regarding
the
multicom-ponent
variants.
Herein,
we
reported
a
copper-Box
system
for
three-component
vinylarenes
1,3-enynes,
with
oxime
carbonates
aryl
boronic
acids.
The
proceed
under
practical
conditions
in
absence
or
presence
visible-light
irradiation,
affording
chiral
1,1-diarylalkanes,
benzylic
alkynes
allenes
good
enantioselectivities.
Mechanistic
studies
imply
that
copper/Box
complexes
play
dual
role
both
radical
generation
ensuing
cross-coupling.
In
cases
irradiation
could
improve
activity
complex
toward
initial
generation,
enabling
better
efficiency
match
between
formation
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(17), С. 4849 - 4856
Опубликована: Янв. 1, 2024
An
electrochemically
driven,
Cp*Ir(
iii
)-catalyzed
method
for
alkenyl
and
aromatic
C(sp
2
)–H
activation
coupling
with
alkynes
the
synthesis
of
biologically
useful
quaternary
ammonium
salts
under
mild
conditions
is
demonstrated.
