Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июль 5, 2024
Abstract
Direct
reduction
of
unactivated
alkyl
halides
for
C(sp3)-N
couplings
under
mild
conditions
presents
a
significant
challenge
in
organic
synthesis
due
to
their
low
potential.
Herein,
we
introduce
an
situ
formed
pyridyl-carbene-ligated
copper
(I)
catalyst
that
is
capable
abstracting
halide
atom
and
generating
radicals
general
visible
light.
Control
experiments
confirmed
the
mono-pyridyl-carbene-ligated
complex
active
species
responsible
catalysis.
Mechanistic
investigations
using
transient
absorption
spectroscopy
across
multiple
decades
timescales
revealed
ultrafast
intersystem
crossing
(260
ps)
photoexcited
complexes
into
long-lived
triplet
excited
states
(>2
μs).
The
non-Stern-Volmer
quenching
dynamics
triplets
by
suggests
association
between
halides,
thereby
facilitating
abstraction
atoms
via
inner-sphere
single
electron
transfer
(SET),
rather
than
outer-sphere
SET,
formation
subsequent
cross
couplings.
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.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(13), С. 5287 - 5299
Опубликована: Янв. 1, 2022
This
review
summarizes
the
different
applications
and
underlying
concepts
that
are
applied
for
Cu(
i
)-
or
ii
)-photocatalyzed
difunctionalizations
of
alkenes.
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.
Science,
Год журнала:
2023,
Номер
381(6662), С. 1072 - 1079
Опубликована: Сен. 7, 2023
The
step
that
cleaves
the
carbon-halogen
bond
in
copper-catalyzed
cross-coupling
reactions
remains
ill
defined
because
of
multiple
redox
manifolds
available
to
copper
and
instability
high-valent
product
formed.
We
report
oxidative
addition
α-haloacetonitrile
ionic
neutral
copper(I)
complexes
form
previously
elusive
but
here
fully
characterized
copper(III)
complexes.
stability
these
stems
from
strong
Cu−CF
3
high
barrier
for
C(
CF
)−C(
CH
2
CN
)
bond-forming
reductive
elimination.
mechanistic
studies
we
performed
suggest
proceeds
by
means
two
different
pathways:
an
S
N
2-type
substitution
complex
a
halogen-atom
transfer
complex.
observed
pronounced
ligand
acceleration
addition,
which
correlates
with
couplings
azoles,
amines,
or
alkynes
alkyl
electrophiles.
Chemical Reviews,
Год журнала:
2023,
Номер
123(20), С. 11817 - 11893
Опубликована: Окт. 4, 2023
Enantioconvergent
catalysis
has
expanded
asymmetric
synthesis
to
new
methodologies
able
convert
racemic
compounds
into
a
single
enantiomer.
This
review
covers
recent
advances
in
transition-metal-catalyzed
transformations,
such
as
radical-based
cross-coupling
of
alkyl
electrophiles
with
nucleophiles
or
alkylmetals
and
reductive
two
mainly
under
Ni/bis(oxazoline)
catalysis.
C–H
functionalization
can
be
performed
an
enantioconvergent
manner.
Hydroalkylation
alkenes,
allenes,
acetylenes
is
alternative
reactions.
Hydrogen
autotransfer
been
applied
amination
alcohols
C–C
bond
forming
reactions
(Guerbet
reaction).
Other
metal-catalyzed
involve
addition
allylic
systems
carbonyl
compounds,
propargylation
phenols,
3-bromooxindoles,
allenylation
allenolates
propargyl
bromides,
hydroxylation
1,3-dicarbonyl
compounds.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(13)
Опубликована: Фев. 1, 2023
A
method
for
direct
access
to
enantioenriched
benzylic
amides
and
carbamate-protected
primary
benzylamines
by
C-H
functionalization
is
reported.
The
substrate
used
as
limiting
reagent
with
only
a
small
excess
of
the
unactivated
amide
or
carbamate
nucleophile.
enantioselective
intermolecular
dehydrogenative
C-N
bond
formation
enabled
combination
chiral
copper
catalyst,
photocatalyst,
an
oxidant,
it
takes
place
under
mild
conditions,
which
allow
broad
scope.
compatible
late-stage
functionalization,
provides
easy
15
N-labeled
amines
starting
from
cheap
NH4
Cl.
