ACS Catalysis,
Год журнала:
2025,
Номер
15(3), С. 2212 - 2221
Опубликована: Янв. 23, 2025
Despite
recent
advances
in
enantioselective
radical
coupling
with
strained
cyclic
rings,
asymmetric
reactions
triggered
by
unstrained
motifs
remain
rare.
Herein,
we
report
a
mild
and
general
strategy
for
activating
diverse
set
of
readily
available
alcohols
the
remote
site-specific
allylic
alkylation
ketones
through
combination
photoredox-mediated
proton-coupled
electron
transfer
chiral
chromium
catalysis.
This
newly
developed
dual
catalytic
system
exhibits
extensive
applicability,
operates
under
conditions,
offers
straightforward
operation,
demonstrates
tolerance
to
functional
groups.
The
open-shell
has
also
been
applied
late-stage
modification
complex
drug
natural
product
derivatives
high
levels
enantioselectivity.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(22), С. 12808 - 12827
Опубликована: Янв. 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.
Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Март 22, 2021
Abstract
The
intermolecular
three-component
alkene
vicinal
dicarbofunctionalization
(DCF)
reaction
allows
installation
of
two
different
carbon
fragments.
Despite
extensive
investigation
into
its
ionic
chemistry,
the
enantioseletive
radical-mediated
versions
DCF
reactions
remain
largely
unexplored.
Herein,
we
report
an
intermolecular,
enantioselective
radical
olefins
enabled
by
merger
addition
and
cross-coupling
using
photoredox
copper
dual
catalysis.
Key
to
success
this
protocol
relies
on
chemoselective
acyl
cyanoalkyl
radicals,
generated
in
situ
from
redox-active
oxime
esters
a
photocatalytic
N-centered
iminyl
radical-triggered
C-C
bond
cleavage
event,
onto
alkenes
form
new
radicals.
Single
electron
metalation
such
newly
formed
radicals
TMSCN-derived
L1
Cu(II)(CN)
2
complex
leads
asymmetric
cross-coupling.
This
process
proceeds
under
mild
conditions,
tolerates
diverse
range
functionalities
synthetic
handles,
leading
valuable
optically
active
β
–cyano
ketones
alkyldinitriles,
respectively,
highly
manner
(>60
examples,
up
97%
ee).
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:
2023,
Номер
145(34), С. 18753 - 18759
Опубликована: Авг. 15, 2023
The
asymmetric
difunctionalization
of
alkenes,
a
method
transforming
readily
accessible
alkenes
into
enantioenriched
chiral
structures
high
value,
has
long
been
focal
point
organic
synthesis.
Despite
tremendous
efforts
in
this
domain,
it
remains
considerable
challenge
to
devise
enantioselective
oxidative
dicarbofunctionalization
even
though
these
transformations
can
utilize
stable
and
unfunctionalized
functional
group
donors.
In
context,
we
report
herein
photoelectrocatalytic
for
the
heteroarylcyanation
aryl
which
employs
heteroarenes
through
C-H
functionalization.
photoelectrochemical
catalysis
(PEAC)
combines
photoredox
electrocatalysis
facilitate
formation
two
C-C
bonds
operating
via
hydrogen
(H2)
evolution
obviating
need
external
chemical
oxidants.
Nature Catalysis,
Год журнала:
2024,
Номер
7(6), С. 655 - 665
Опубликована: Апрель 29, 2024
Abstract
The
development
of
novel
strategies
to
rapidly
construct
complex
chiral
molecules
from
readily
available
feedstocks
is
a
long-term
pursuit
in
the
chemistry
community.
Radical-mediated
alkene
difunctionalizations
represent
an
excellent
platform
towards
this
goal.
However,
asymmetric
versions
remain
highly
challenging,
and
more
importantly,
examples
featuring
simple
hydrocarbons
as
reaction
partners
are
elusive.
Here
we
report
three-component
dicarbofunctionalization
capitalizing
on
direct
activation
C(
sp
3
)–H
bonds
through
combination
photocatalysed
hydrogen
atom
transfer
nickel
catalysis.
This
protocol
provides
efficient
for
installing
two
vicinal
carbon–carbon
across
alkenes
atom-economic
fashion,
providing
wide
array
high-value
α-aryl/alkenyl
carbonyls
phosphonates,
well
1,1-diarylalkanes
ubiquitous
alkane,
ether
alcohol
feedstocks.
method
exhibits
operational
simplicity,
broad
substrate
scope
regioselectivity,
chemoselectivity
enantioselectivity.
compatibility
with
bioactive
motifs
expedient
synthesis
pharmaceutically
relevant
highlight
synthetic
potential
protocol.
We
describe
an
efficient
acyl
esterification
method
for
alkenes
utilizing
acyloxime
esters
as
bifunctional
reagents
featuring
radical
acylation
and
congested
C–O
bond
formation.
This
approach
is
characterized
by
mild
photoredox
conditions,
high
step
atom
economy,
a
broad
substrate
scope,
excellent
regioselectivity.
A
variety
of
valuable
α-acyl
hindered
alcohol
esters,
including
those
obtained
via
gram-scale
synthesis
late-stage
functionalization
pharmaceutical
molecules,
were
presented,
demonstrating
its
synthetic
potential
practicability.
Green Chemistry,
Год журнала:
2021,
Номер
23(15), С. 5379 - 5393
Опубликована: Янв. 1, 2021
The
key
advances
in
the
field
of
metallaphotoredox-catalyzed
multicomponent
couplings
recent
years
are
highlighted
this
review.
To
better
meet
needs
modern
chemistry,
further
research
outlooks
were
also
proposed.
Chemical Communications,
Год журнала:
2021,
Номер
58(6), С. 730 - 746
Опубликована: Дек. 8, 2021
This
article
provides
a
comprehensive
perspective
on
three-component
1,2-dicarbofunctionalization
of
alkenes
involving
alkyl
radicals,
which
generated
from
structurally
diverse
electrophilic
and
nucleophilic
precursors
under
mild
conditions.
