Photoredox/Cr-catalyzed enantioselective radical-polar crossover transformation via C-H functionalization
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Фев. 4, 2025
Asymmetric
multicomponent
reactions
that
aim
to
control
multiple
chiral
centers
with
high
selectivity
in
a
single
step
remain
an
on-gonging
challenge.
The
realm
of
enantioselective
radical-polar
crossover
transformation
achieved
through
C-H
Functionalization
has
yet
be
fully
explored.
Herein,
we
present
successful
description
photoredox/Cr-catalyzed
three-component
(hetero)arylalkylation
1,3-dienes
functionalization.
A
diverse
array
homoallylic
alcohols
could
obtained
good
excellent
yields,
accompanied
by
outstanding
enantioselectivity.
asymmetric
build
two
simultaneously
and
demonstrates
broad
substrate
tolerance,
accommodating
various
drug-derived
aldehydes,
(hetero)aromatics,
1,3-diene
derivatives.
Preliminary
mechanistic
studies
indicate
the
involvement
radical
intermediate,
allylic
chromium
species
reacting
aliphatic
aromatic
aldehydes
Zimmerman–Traxler
transition
states
enabled
dual
photoredox
catalysis.
ongoing
Here,
authors
photoredox-
chromium-catalyzed
Язык: Английский
Recent advances in copper-catalyzed multicomponent reactions with photoinduction
Coordination Chemistry Reviews,
Год журнала:
2025,
Номер
528, С. 216428 - 216428
Опубликована: Янв. 4, 2025
Язык: Английский
Photoredox/Copper-Catalyzed One-Pot Aminoalkylation/Cyclization of Alkenes with Primary Amines to Synthesize Polysubstituted γ-Lactams
Organic Letters,
Год журнала:
2024,
Номер
26(4), С. 845 - 849
Опубликована: Янв. 22, 2024
Visible-light-driven
chemical
transformation
has
emerged
as
a
powerful
tool
for
the
synthesis
of
γ-lactams.
However,
during
this
transformation,
α-bromoimides
need
to
be
pre-prepared.
Herein,
we
report
photoreodox/copper-catalyzed
one-pot
three-component
reaction
alkenes
with
primary
amines
construction
In
orthoquinones
were
generated
via
photocatalytic
pathway,
followed
by
attack
Cu–amido
complexes
and
intramolecular
cyclization
give
This
method
represents
simple
synthetic
route
displaying
broad
functional
group
tolerance,
including
substrates
bearing
alcohols,
ketones,
heterocycles,
esters,
halides,
alkynes,
nitriles,
ethers,
etc.
Язык: Английский
Photocatalysis Meets Copper Catalysis: A New Opportunity for Asymmetric Multicomponent Radical Cross-Coupling Reactions
Accounts of Chemical Research,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 13, 2024
ConspectusIn
recent
years,
radical-mediated
cross-coupling
reactions
have
emerged
as
a
compelling
strategy
for
achieving
rich
diversity
in
molecular
topologies
under
benign
conditions.
However,
the
inherent
high
reactivity
of
radicals
presents
considerable
challenges
controlling
reaction
pathways
and
selectivity,
which
often
results
limited
range
substrates
constrained
profile.
Given
capacity
visible-light
photoredox
catalysis
to
generate
wide
variety
reactive
radical
ions
controlled
manner
propensity
copper
complexes
toward
species,
we
envisaged
that
synergy
between
chiral
catalysts
photoactive
would
pave
way
developing
innovative
strategies.
This
integration
is
poised
unlock
broad
spectrum
enantioselective
multicomponent
reactions.In
this
Account,
describe
our
insights
efforts
realm
reactions.
These
advancements
been
achieved
through
application
dual
photoredox/copper
or
bifunctional
visible
light
irradiation.
Our
work
systematically
divided
into
two
sections
based
on
activation
modes.
The
first
section
focuses
photoinduced
copper-catalyzed
C-C
C-O
bond
formation
addition/nucleophilic
trap
sequence.
discussion
particularly
concentrated
asymmetric
carbocyanation
carboarylation
vinylarenes,
1,3-enynes,
1,3-dienes.
findings
underscore
irradiation
with
can
adeptly
modulate
pace
generation,
thus
orchestrating
consecutive
stages
ensuring
attainment
both
chemo-
stereoselectivity.
In
domain
formation,
leveraging
carboxylic
acids
nucleophilic
oxygen
source,
introduce
suite
esterification
benzylic,
allylic,
propargylic
radicals.
are
derived
from
precursors,
showcasing
versatility
approach.
following
highlights
discovery
field
catalysis,
enables
three-component
transformations
via
direct
aromatic
alkenes.
methodology
begins
generation
formal
distonic
anions
photocatalytic
single-electron
reduction
alkenes,
thus,
enabling
orthogonal
reactivity.
Employing
H
Язык: Английский
Sustainable click reactions: Use of greener reaction media in the synthesis of 1,2,3-triazoles
Tetrahedron,
Год журнала:
2024,
Номер
157, С. 133964 - 133964
Опубликована: Март 31, 2024
Язык: Английский
Ni-catalyzed enantioselective three-component reductive alkylacylation of alkenes: modular access to structurally complex α-amino ketones
Chemical Science,
Год журнала:
2024,
Номер
15(37), С. 15489 - 15495
Опубликована: Янв. 1, 2024
Nickel-catalyzed
three-component
reductive
dicarbofunctionalization
of
activated
olefins
(enamides)
is
presented.
Язык: Английский
Ni-Catalyzed Enantioselective Three-Component Reductive Alkylacylation of Enamides
Опубликована: Июнь 21, 2024
Chiral
alpha-amino
ketones
have
found
extensive
applications
as
functional
molecules.
A
nickel-catalyzed,
enantioselective,
and
fully
intermolecular
three-component
1,2-alkylacylation
of
N-acyl
enamides
has
been
realized
with
tertiary
alkyl
bromides
carboxylic
acid-derived
electrophiles
the
coupling
reagents.
This
reductive
strategy
is
operationally
simple,
exhibiting
broad
substrate
scope
excellent
group
tolerance
using
readily
available
starting
materials
allowing
rapid
access
to
structurally
complex
α-amino
ketone
derivatives
in
high
enantioselectivity.
suitable
chiral
biimidazoline
ligand
together
additional
chelation
amide
carbonyl
a
Ni
intermediate
facilitates
enantioselective
control
by
suppressing
background
reaction,
accounting
for
Mechanistic
studies
indicated
intermediacy
radical
species.
Язык: Английский
Photo‐induced three‐component reaction for the construction of α‐tertiary amino acid derivatives
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(70)
Опубликована: Сен. 21, 2024
Abstract
The
synthesis
of
α‐tertiary
amino
acids
(ATAAs),
which
are
pivotal
components
in
natural
metabolism
and
pharmaceutical
innovation,
continues
to
attract
significant
research
interest.
Despite
substantial
advancements,
the
pursuit
a
facile,
versatile,
resource‐efficient
methodology
remains
an
area
active
development.
In
this
work,
we
introduce
visible
light‐triggered
three‐component
reaction
involving
readily
available
nitrosoarenes,
N
‐acyl
pyrazoles,
allyl
or
(bromomethyl)benzenes
under
mild
conditions.
This
approach
enables
straightforward
assembly
wide
array
ATAA
derivatives
(42
examples)
commendably
high
yields
(up
89
%).
Mechanistic
investigations
elucidate
that
proceeds
through
dehydration
condensation
between
nitrosoarenes
pyrazoles
generate
ketimine
intermediates.
is
followed
by
light‐driven
halogen
atom
transfer
(XAT)
process
radical
addition,
culminating
formation
desired
products.
showcases
excellent
functional
group
compatibility
late‐stage
derivatization
potential,
offering
new
insights
avenues
for
analogs.
Язык: Английский