ACS Catalysis,
Год журнала:
2024,
Номер
14(16), С. 11974 - 11989
Опубликована: Июль 26, 2024
Photoactive
copper
complexes
have
gained
significant
attention
due
to
their
photocatalytic
activities.
Different
homogeneous
Cu(I)
complexes,
Cu(II)
and
heterogeneous
copper-based
photocatalysts
been
investigated
utilized
in
a
broad
spectrum
of
organic
transformations.
These
applications
span
radical
additions,
C–C
bond
C–heteroatom
cross-couplings,
aerobic
oxidative
reactions,
kinetic
resolutions.
This
review
summarizes
the
advancements
this
dynamic
field
visible-light-induced,
excited-state
copper-catalyzed
reactions
over
recent
years.
It
is
organized
according
type
excited
species
involved
provides
perspective
on
current
future
developments.
Chemical Reviews,
Год журнала:
2022,
Номер
122(22), С. 16365 - 16609
Опубликована: Ноя. 9, 2022
Photocatalyzed
and
photosensitized
chemical
processes
have
seen
growing
interest
recently
become
among
the
most
active
areas
of
research,
notably
due
to
their
applications
in
fields
such
as
medicine,
synthesis,
material
science
or
environmental
chemistry.
Among
all
homogeneous
catalytic
systems
reported
date,
photoactive
copper(I)
complexes
been
shown
be
especially
attractive,
not
only
alternative
noble
metal
complexes,
extensively
studied
utilized
recently.
They
are
at
core
this
review
article
which
is
divided
into
two
main
sections.
The
first
one
focuses
on
an
exhaustive
comprehensive
overview
structural,
photophysical
electrochemical
properties
mononuclear
typical
examples
highlighting
critical
structural
parameters
impact
being
presented
enlighten
future
design
complexes.
second
section
devoted
application
(photoredox
catalysis
organic
reactions
polymerization,
hydrogen
production,
photoreduction
carbon
dioxide
dye-sensitized
solar
cells),
illustrating
progression
from
early
current
state-of-the-art
showcasing
how
some
limitations
can
overcome
with
high
versatility.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(38), С. 17319 - 17329
Опубликована: Сен. 1, 2022
The
enantioconvergent
cross-coupling
of
racemic
alkyl
halides
represents
a
powerful
tool
for
the
synthesis
enantioenriched
molecules.
In
this
regard,
first-row
transition
metal
catalysis
provides
suitable
mechanism
stereoconvergence
by
converting
to
prochiral
radical
intermediates
owing
their
good
single-electron
transfer
ability.
contrast
noble
development
chiral
nickel
catalyst,
copper-catalyzed
is
less
studied.
Besides
enantiocontrol
issue,
major
challenge
arises
from
weak
reducing
capability
copper
that
slows
reaction
initiation.
Recently,
significant
efforts
have
been
dedicated
basic
research
aimed
at
developing
ligands
halides.
This
perspective
will
discuss
advances
in
burgeoning
area
with
particular
emphasis
on
strategic
anionic
ligand
design
tune
initiation
under
thermal
conditions
our
group.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 2, 2025
Regiodivergent
asymmetric
synthesis
represents
a
transformative
strategy
for
the
efficient
generation
of
structurally
diverse
chiral
products
from
single
set
starting
materials,
significantly
enriching
their
enantiomeric
composition.
However,
design
radical-mediated
regiodivergent
and
enantioselective
reactions
that
can
accommodate
wide
range
functional
groups
substrates
has
posed
significant
challenges.
The
obstacles
primarily
lie
in
switching
regioselectivity
achieving
high
enantiodiscrimination,
especially
when
dealing
with
high-energy
intermediates.
To
address
these
issues,
we
have
developed
new
catalytic
system
integrates
photoinduced
hydrogen
atom
transfer
(HAT)
copper
catalysis,
involving
fine-tuning
ligands,
additives,
other
reaction
parameters.
facilitates
cross-couplings
between
N-aryl
glycine
ester/amide
derivatives
abundant
hydrocarbon
feedstocks
through
strong
C(sp3)–H
bond
activation.
This
approach
allows
controlled
stereoselective
formation
C(sp3)–C(sp3)
C(sp3)–N
bonds,
yielding
rich
variety
C-
or
N-alkylated
esters
amides
commendable
yields
(up
to
92%
yield),
exclusive
regioselectivities
(typically
>20:1
rr),
enantioselectivities
96%
ee).
Our
methodology
not
only
provides
promising
avenue
incorporation
alkyl
functionalities
onto
specific
sites
biologically
molecules
but
also
offers
practical
while
simultaneously
induction
within
photochemical
reactions.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(27), С. 12052 - 12061
Опубликована: Июнь 29, 2022
Activation
of
aryl
chlorides
in
cross-coupling
reactions
is
a
long-standing
challenge
organic
synthesis
that
great
interest
to
industry.
Ultrasmall
(<3
nm),
atomically
precise
nanoclusters
(NCs)
are
considered
one
the
most
promising
catalysts
due
their
high
surface
area
and
unsaturated
active
sites.
Herein,
we
introduce
copper
nanocluster-based
catalyst,
[Cu61(StBu)26S6Cl6H14]
(Cu61NC)
enables
C–N
bond-forming
under
visible-light
irradiation
at
room
temperature.
A
range
N-heterocyclic
nucleophiles
electronically
sterically
diverse
aryl/hetero
react
this
new
Cu61NC-catalyzed
process
afford
coupling
products
good
yields.
Mechanistic
studies
indicate
single-electron-transfer
(SET)
between
photoexcited
Cu61NC
complex
halide
C–N-arylation
reaction.
