A
new
three-component
1,2-perfluoroalkyl
trifluoromethylthiolation
of
alkenes
via
dual
photoredox/copper
catalysis
has
been
established,
affording
a
variety
CnF2n+1/CF3S-containing
molecules
under
mild
conditions
in
redox-neutral
manner.
This
protocol
exhibits
excellent
functional
group
tolerance,
broad
compatibility
with
various
and
perfluoroalkyl
iodides,
potential
utility
the
modification
bioactive
molecules.
ACS Catalysis,
Год журнала:
2022,
Номер
12(18), С. 11216 - 11225
Опубликована: Сен. 1, 2022
A
strategy
for
both
cross-electrophile
coupling
and
1,2-dicarbofunctionalization
of
olefins
has
been
developed.
Carbon-centered
radicals
are
generated
from
alkyl
bromides
by
merging
benzophenone
hydrogen
atom
transfer
(HAT)
photocatalysis
silyl
radical-induced
halogen
(XAT)
subsequently
intercepted
a
nickel
catalyst
to
forge
the
targeted
C(sp3)-C(sp2)
C(sp3)-C(sp3)
bonds.
The
mild
protocol
is
fast
scalable
using
flow
technology,
displays
broad
functional
group
tolerance,
amenable
wide
variety
medicinally
relevant
moieties.
Mechanistic
investigations
reveal
that
ketone
catalyst,
upon
photoexcitation,
responsible
direct
activation
silicon-based
XAT
reagent
(HAT-mediated
XAT)
furnishes
radical
ultimately
involved
in
turnover
catalytic
cycle.
ACS Catalysis,
Год журнала:
2022,
Номер
12(6), С. 3279 - 3285
Опубликована: Фев. 25, 2022
A
visible
light-driven
photoredox-catalyzed
and
copper(II)-assisted
three-component
radical
addition/hydroxylation
reaction
of
alkenes,
sulfur
ylides,
water
is
reported.
This
process
shows
broad
substrate
scope
high
functional
group
tolerance,
with
respect
to
both
readily
available
ylides
providing
high-yielding
practical
access
valuable
γ-hydroxy
carbonyl
compounds.
Key
the
success
controlled
generation
α-carbonyl
carbon
radicals
from
via
sulfonium
salts
by
a
visible-light-driven
proton-coupled
electron
transfer
(PCET)
strategy
in
mixture
2,2,2-trifluoroethanol/CH2Cl2.
Addition
Cu(TFA)2·H2O
helps
accelerate
radical-cation
crossover
improve
efficiency.
Mechanistic
studies
suggest
that
hydroxy
moiety
products
stems
water.
study
also
builds
up
platform
for
further
investigation
into
synthetic
chemistry
ylides.
ACS Catalysis,
Год журнала:
2023,
Номер
13(7), С. 4111 - 4119
Опубликована: Март 10, 2023
The
nickel-catalyzed
multicomponent
dicarbofunctionalization
of
alkenes
represents
one
the
most
straightforward
approaches
to
complex
organofluorine
compounds.
However,
catalytic
carbofluoroalkylation
electron-deficient
remains
underdeveloped.
Here,
we
report
a
three-component
aryldifluoroalkylation
industry-relevant
acrylonitrile
and
acrylate
with
arylboronic
acids
difluoroalkyl
halides.
reaction
can
extend
four-component
carbonylation
under
1
atm
CO
gas.
This
modular
synthesis
features
synthetic
convenience,
high
functional
group
tolerance,
simple
components
construct
difluoroalkylated
compounds
expediently.
utility
has
also
been
demonstrated
by
diversified
transformations
resulting
products
into
medicinal
interest
fluorinated
Organic Letters,
Год журнала:
2023,
Номер
25(9), С. 1441 - 1446
Опубликована: Фев. 23, 2023
A
visible-light-photocatalyzed
1,2-arylalkylation
of
N-(arylsulfonyl)acrylamides
with
ketone-based
dihydroquinazolinones
is
described.
The
formal
C-C
bond
cleavage
aliphatic
ketones
unified
tandem
radical
alkylation/1,4-aryl
migration/desulfonylation
to
forge
two
different
types
vicinal
bonds
and
construct
an
all-carbon
quaternary
α-stereocenter,
thus
enhancing
the
carbogenic
complexity
tolerating
diverse
functionalities.
Additional
telescopic
synthesis
product
diversification,
this
method
features
a
dicarbofunctionalization
conjugated
nucleophilic
alkyl
precursor
(dihydroquinazolinone)
utilizing
oxygen
as
green
oxidant
at
ambient
temperature.
Chemical Science,
Год журнала:
2024,
Номер
15(11), С. 4031 - 4040
Опубликована: Янв. 1, 2024
A
free-radical
approach
featuring
an
intramolecular
aryl
migration
has
significantly
expanded
the
scope
for
alkyl–(hetero)arylation
of
simple
olefins.
It
was
also
leveraged
as
key
step
in
a
new
synthesis
recently
approved
pharmaceutical.
Cell Reports Physical Science,
Год журнала:
2024,
Номер
5(2), С. 101831 - 101831
Опубликована: Фев. 1, 2024
Nickel-catalyzed
radical
relayed
dicarbofunctionalizations
of
olefins,
utilizing
carbon
electrophiles
as
coupling
partners,
present
a
powerful
strategy
for
the
streamlined
construction
aliphatic
structures.
However,
traditional
solution-phase
methods
encounter
challenges
such
need
bulk
solvents,
limited
long
reaction
times,
and
air-/moisture-sensitive
reagents.
As
an
alternative
strategy,
ball-mill-enabled
metal-catalyzed
cross-coupling
reactions
have
gained
attention
due
to
their
high
reactivity
atomic
efficiency.
While
many
are
single-
two-component
methodologies,
three-component
solid-state
remain
relatively
scarce.
In
this
work,
we
report
first,
our
knowledge,
ball-milling-enabled
Ni-catalyzed
reductive
dicarbofunctionalization
alkenes.
Two
distinct
readily
available
electrophiles,
Csp2
Csp3
halides,
simultaneously
installed
across
variety
olefins
at
room
temperature
in
highly
regioselective
manner
withing
1.5
h.
By
harnessing
benefits
ball
milling
reactions,
anticipate
further
advancements
sustainable
efficient
synthetic
methodologies.
Chemical Communications,
Год журнала:
2024,
Номер
60(68), С. 8946 - 8977
Опубликована: Янв. 1, 2024
Alkene
carbofunctionalization
reactions
have
great
potential
for
synthesizing
complex
molecules
and
constructing
structures
in
natural
products
medicinal
chemistry.
Recently,
dual
photoredox/nickel
catalysis
has
emerged
as
a
novel
strategy
alkene
carbofunctionalization.
Nickel
offers
numerous
advantages
over
other
transition
metals,
such
cost-effectiveness,
abundance,
low
toxicity,
moreover,
it
many
oxidation
states.
catalysts
exhibit
excellent
catalytic
activity
photoredox/transition
metal
catalysis,
facilitating
the
formation
of
carbon-carbon
or
carbon-heteroatom
bonds
organic
transformations.
This
review
highlights
latest
advancements
photoredox/nickel-catalyzed
carbofunctionalizations
includes
literature
published
from
2020
to
2024.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 15, 2025
Advancements
in
radical
capture
strategies
have
expanded
the
range
of
products
accessible
from
alkenes
through
dealkenylative
synthesis.
These
methods,
however,
are
still
limited,
as
they
rely
on
ozonolysis
to
generate
key
peroxide
intermediates
alkenes.
Ozonolysis
has
several
limitations.
It
is
not
compatible
with
containing
electron-rich
aromatics.
also
inapplicable
certain
alkene
substitution
patterns
context
Additionally,
it
struggles
sterically
hindered
alkenes,
internal
nucleophiles
and
electrophiles,
allylic
alcohols.
In
this
paper,
using
Isayama-Mukaiyama
peroxidation
(IMP),
we
address
limitations
rescue
previously
inaccessible
substrates
broaden
applicability
functionalization.
particular,
apply
IMP
hydrodealkenylation
describe
a
novel
hydrogenation
condition─employing
catalytic
[FeIII],
benzenethiol,
γ-terpinene
refluxing
methanol─to
resolve
β-scission
issues
associated
IMP-generated
alkyl
silylperoxides.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(11), С. 2773 - 2781
Опубликована: Янв. 1, 2023
A
regio-
and
enantioselective
radical
three-component
coupling
of
1,3-enynes,
oxime
esters,
carboxylic
acids
through
photoinduced
copper
catalysis
is
reported.
