ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(11), P. 7523 - 7528
Published: May 19, 2023
Dual
photoredox–transition-metal
catalysis
has
emerged
as
a
powerful
tool
for
the
development
of
chemical
transformations.
However,
its
application
in
selective
difunctionalization
1,3-dienes
remains
essentially
unexploited.
By
synergistic
action
photoredox
and
copper
catalysts,
we
report
herein
an
enantioselective
1,2-amidocyanation
1,3-dienes.
Visible-light
irradiation
chloroform
solution
conjugated
dienes,
N-Boc-amidopyridinium
salts,
TMSCN
presence
catalytic
amount
fac-Ir(ppy)3,
Cu(OTf)2·xH2O,
chiral
Box
ligand
affords
three-component
adducts
good
to
high
yields
with
regio-
enantioselectivities.
A
L*CuCN
complex,
fully
characterized
spectroscopically
confirmed
by
X-ray
crystallographic
analysis,
is
able
catalyze
transformation,
therefore
supporting
inner-sphere
cyanide
transfer
pathway.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(33), P. 13382 - 13392
Published: Aug. 10, 2021
The
construction
of
carbon–heteroatom
bonds
is
one
the
most
active
areas
research
in
organic
chemistry
because
function
molecules
often
derived
from
presence
heteroatoms.
Although
considerable
advances
have
recently
been
achieved
radical-involved
catalytic
asymmetric
C–N
bond
formation,
there
has
little
progress
corresponding
C–O
bond-forming
processes.
Here,
we
describe
a
photoinduced
copper-catalyzed
cross-coupling
readily
available
oxime
esters
and
1,3-dienes
to
generate
diversely
substituted
allylic
with
high
regio-
enantioselectivity
(>75
examples;
up
95%
ee).
reaction
proceeds
at
room
temperature
under
excitation
by
purple
light-emitting
diodes
(LEDs)
features
use
single,
earth-abundant
copper-based
chiral
catalyst
as
both
photoredox
for
radical
generation
source
induction
coupling.
Combined
experimental
density
functional
theory
(DFT)
computational
studies
suggest
formation
π-allylcopper
complexes
redox-active
bifunctional
reagents
through
radical–polar
crossover
process.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(22), P. 12808 - 12827
Published: Jan. 1, 2021
Transition
metal-catalysed
asymmetric
coupling
has
been
established
as
a
robust
tool
for
constructing
complex
organic
molecules.
Although
this
area
extensively
studied,
the
development
of
efficient
protocols
to
construct
stereogenic
centres
with
excellent
regio-
and
enantioselectivities
is
highly
desirable
remains
challenging.
Asymmetric
transition
metal
catalysis
light
intervention
provides
practical
alternative
strategy
current
methods
considerably
expands
synthetic
utility
result
abundant
feedstocks
mild
conditions.
This
tutorial
review
comprehensively
summarizes
recent
advances
in
transition-metal-catalysed
reactions
intervention;
particular,
concise
analysis
substrate
scope
mechanistic
scenarios
governing
stereocontrol
discussed.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(42), P. 22956 - 22962
Published: Aug. 18, 2021
Abstract
Kharasch–Sosnovsky
reaction
is
one
of
the
most
powerful
methods
for
allylic
oxidation
alkenes.
However,
inherent
radical
mechanism
and
use
peroxides
as
both
oxidants
oxygen
nucleophiles
render
dearth
universal
catalytic
systems
highly
enantioselective
variants
limited
scope.
Herein,
an
alternative
to
asymmetric
that
utilized
a
chiral
copper
catalyst
purple‐LED
irradiation
enable
three‐component
coupling
1,3‐dienes,
oxime
esters,
carboxylic
acids
reported.
This
protocol
features
mild
conditions,
remarkable
scope
functional
group
tolerance
evidenced
by
>80
examples
utility
in
late‐stage
modification
pharmaceuticals
natural
products.
Detailed
mechanistic
studies
provide
evidences
radical‐based
pathway.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(13), P. 5287 - 5299
Published: Jan. 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,
Journal Year:
2022,
Volume and Issue:
144(18), P. 8347 - 8354
Published: April 28, 2022
Grignard
addition
is
one
of
the
most
important
methods
used
for
syntheses
alcohol
compounds
and
has
been
known
over
a
hundred
years.
However,
research
on
asymmetric
catalysis
relies
use
organometallic
nucleophiles.
Here,
we
report
first
visible-light-induced
cobalt-catalyzed
reductive
Grignard-type
synthesizing
chiral
benzyl
alcohols
(>50
examples,
up
to
99%
yield,
ee).
This
methodology
advantages
mild
reaction
conditions,
good
functionality
tolerance,
excellent
enantiocontrol,
avoidance
mass
metal
wastes,
precious
catalysts.
Kinetic
realization
studies
suggested
that
migratory
insertion
an
aryl
cobalt
species
into
aldehyde
was
rate-determining
step
reaction.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(12), P. 6944 - 6952
Published: March 15, 2023
Enantioselective
metallaphotoredox
catalysis,
which
combines
photoredox
catalysis
and
asymmetric
transition-metal
has
become
an
effective
approach
to
achieve
stereoconvergence
under
mild
conditions.
Although
many
impressive
synthetic
approaches
have
been
developed
access
central
chirality,
the
construction
of
axial
chirality
by
still
remains
underexplored.
Herein,
we
report
two
visible
light-induced
cobalt-catalyzed
reductive
couplings
biaryl
dialdehydes
synthesize
axially
chiral
aldehydes
(60
examples,
up
98%
yield,
>19:1
dr,
>99%
ee).
This
protocol
shows
good
functional
group
tolerance,
broad
substrate
scope,
excellent
diastereo-
enantioselectivity.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(13), P. 6040 - 6049
Published: March 24, 2022
Axially
chiral
biaryls
and
heterobiaryls
constitute
the
most
represented
subclass
of
atropisomers
with
prevalence
in
natural
products,
bioactive
compounds,
privileged
ligand/catalysts,
optically
pure
materials.
Despite
many
ionic
protocols
for
their
construction,
radical-based
variants
represent
another
highly
desirable
intriguing
strategy
but
are
far
less
developed.
Moreover,
efficient
synthesis
axially
heterobiaryl
molecules,
especially
ones
having
multiple
heteroatoms
other
types
elements,
through
radical
routes
remains
extremely
limited.
We
herein
disclose
first
catalytic
asymmetric,
metal-free
construction
centrally
by
Minisci
reaction
5-arylpyrimidines
α-amino
acid-derived
redox-active
esters.
This
is
enabled
use
4CzIPN
as
an
organic
photoredox
catalyst
conjunction
a
phosphoric
acid
catalyst.
The
achieved
variety
interesting
featuring
union
α-branched
amine
generally
excellent
regio-,
diastereo-,
enantioselectivity
(up
to
82%
yield;
>19:1
dr;
>99%
ee).
finding
also
builds
up
new
platform
development
desymmetrization
methods
via
radical-involved
atroposelective
functionalization
at
heteroarene
prochiral
heterobiaryls.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(14), P. 7983 - 7991
Published: March 28, 2023
Conjugate
addition
is
among
the
most
important
synthetic
protocols
for
constructing
carbon
skeletons
and
widely
used
to
synthesize
natural
products
drugs.
However,
asymmetric
catalysis
studies
have
mainly
focused
on
stereogenic
centers
arising
from
conjugate
alkenes.
Here,
we
report
first
photoinduced
cobalt-catalyzed
dynamic
kinetic
reductive
reaction
that
enables
formation
of
heterobiaryls
with
axial
chirality
(45
examples,
up
91%
yield
97%
ee).
This
method
features
mild
conditions,
good
functional-group
tolerance,
excellent
enantiomeric
control.
Significantly,
large
amounts
metal
waste
precious
catalysts
can
be
avoided
under
these
conditions.
Migration
chiral
arylcobalt
species
into
alkene
might
rate-determining
step
based
studies.