Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(47), С. 16854 - 16858
Опубликована: Сен. 18, 2019
Abstract
Photochemical
enantioselective
nickel‐catalyzed
cross‐coupling
reactions
are
difficult
to
implement.
We
report
a
visible‐light‐mediated
strategy
that
successfully
couples
symmetrical
anhydrides
and
4‐alkyl
dihydropyridines
(DHPs)
afford
enantioenriched
α‐substituted
ketones
under
mild
conditions.
The
chemistry
does
not
require
exogenous
photocatalysts.
It
is
triggered
by
the
direct
excitation
of
DHPs,
which
act
as
radical
source
reductant,
facilitating
turnover
chiral
catalytic
nickel
complex.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(9), С. 3989 - 3997
Опубликована: Фев. 22, 2022
Chiral
phosphine-containing
skeletons
are
important
motifs
in
bioactive
natural
products,
pharmaceuticals,
chiral
catalysts,
and
ligands.
Herein,
we
report
a
general
modular
platform
to
access
α-aryl
phosphorus
compounds
via
Ni/photoredox-catalyzed
enantioconvergent
reductive
cross-coupling
between
α-bromophosphates
aryl
iodides.
This
dual
catalytic
regime
exhibited
high
efficiency
good
functional
group
compacity.
A
wide
variety
of
substrates
bearing
diverse
set
groups
could
be
converted
into
phosphates
excellent
yields
enantioselectivities.
The
utility
the
method
was
also
demonstrated
by
development
new
phosphine
ligand
synthesis
enzyme
inhibitor
derivatives.
detailed
mechanistic
studies
supported
radical
chain
process
revealed
unique
distinction
compared
with
traditional
cross-coupling.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(4), С. 2351 - 2357
Опубликована: Янв. 17, 2024
Cross-coupling
catalysts
typically
react
and
unite
functionally
distinct
partners
via
sequential
inner-sphere
elementary
steps:
coordination,
migratory
insertion,
reductive
elimination,
etc.
Here,
we
report
a
single
catalyst
that
cross-couples
styrenes
benzyl
bromides
iterative
outer-sphere
metal–ligand-carbon
interactions.
Each
partner
forms
stabilized
radical
intermediate,
yet
heterocoupled
products
predominate.
The
system
is
redox-neutral
and,
thus,
avoids
exogenous
oxidants,
resulting
in
simple
scalable
conditions.
Numerous
variations
of
alkene
hydrobenzylation
are
made
possible,
including
access
to
the
privileged
heterodibenzyl
(1,2-diarylethane)
motif
challenging
quaternary
carbon
variants.
Organic Letters,
Год журнала:
2020,
Номер
22(15), С. 5984 - 5989
Опубликована: Июль 24, 2020
An
efficient,
photoredox-catalyst-free
radical
alkylation
of
quinoxalin-2(1H)-ones
has
been
described.
This
reaction
utilizes
4-alkyl-1,4-dihydropyridines
(R-DHPs)
as
alkyl
precursors
and
acetoxybenziodoxole
(BI-OAc)
an
electron
acceptor
to
undergo
single-electron
transfer
with
photoexcited
R-DHPs.
The
benign
conditions
allow
for
good
compatibility
in
the
scope
both
synthetic
value
protocol
was
also
demonstrated
by
successful
functionalization
natural
products
drug-based
complex
molecules
Organic & Biomolecular Chemistry,
Год журнала:
2019,
Номер
17(38), С. 8673 - 8689
Опубликована: Янв. 1, 2019
Asymmetric
visible-light
photocatalysis
has
recently
drawn
considerable
attention
of
the
scientific
community
owing
to
its
unique
activation
modes
and
significance
for
enantioselective
green
synthesis.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(47), С. 16854 - 16858
Опубликована: Сен. 18, 2019
Abstract
Photochemical
enantioselective
nickel‐catalyzed
cross‐coupling
reactions
are
difficult
to
implement.
We
report
a
visible‐light‐mediated
strategy
that
successfully
couples
symmetrical
anhydrides
and
4‐alkyl
dihydropyridines
(DHPs)
afford
enantioenriched
α‐substituted
ketones
under
mild
conditions.
The
chemistry
does
not
require
exogenous
photocatalysts.
It
is
triggered
by
the
direct
excitation
of
DHPs,
which
act
as
radical
source
reductant,
facilitating
turnover
chiral
catalytic
nickel
complex.
