Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 4, 2024
Difluoromethylene
and
pyridine
cores
are
very
important
structural
units
in
medicinal
chemistry.
Herein,
we
report
the
development
of
photoredox-catalyzed
ring-opening
1,3-alkoxypyridylation
gem-difluorinated
cyclopropanes
using
4-cyanopyrines
alcohols,
employing
cyclopropane
radical
cations
as
key
intermediate.
The
reaction
exhibits
high
regioselectivity
under
mild
conditions
can
also
be
practiced
on
gram-scale
synthesis,
telescoped
reaction,
late-stage
functionalization
biological
molecules.
ChemCatChem,
Journal Year:
2023,
Volume and Issue:
16(5)
Published: Nov. 27, 2023
Abstract
(Hetero)arenes
are
one
kind
of
important
structural
motifs
existed
extensively
in
clinical
pharmaceutics,
pesticides,
and
so
on.
Developing
novel
method
for
introducing
(hetero)aryl
group
through
the
employment
cheap
abundant
feedstocks
has
attracted
considerable
attentions
from
synthetic
community.
In
this
review,
we
summarize
recent
advancements
photoredox‐catalyzed
decyanative
cross‐coupling
reactions
based
on
persistent
aromatic
nitrile‐derived
radical.
We
separate
review
into
redox‐neutral
reductive
according
to
whether
an
external
reducing
agent
is
required.
The
diverse
strategies
overcoming
redox
potential
limitation
photocatalyst
emphasized
discussion
specific
reaction.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(23), P. 16639 - 16643
Published: Nov. 17, 2023
A
radical
hydroalkylative
cyclization
approach
accessing
various
alkenyl
heterocyclic
compounds
was
developed
using
dimethyl
malonate
and
1,6-enynes
in
the
presence
of
visible-light
photoredox
catalysis.
The
use
Ir(dtbbpy)(ppy)2PF6
as
a
photosensitizer
enables
carbon
atom
formation
initiates
cascade
reaction
under
mild
conditions.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
30(12)
Published: Nov. 23, 2023
Abstract
Site‐selective
C(
sp
3
)−H
functionalization
of
unreactive
hydrocarbons
is
always
challenging
due
to
its
inherited
chemical
inertness,
slightly
different
reactivity
various
C−H
bonds,
and
intrinsically
high
bond
dissociation
energies.
Here,
a
site‐selective
alkylation
naphthoquinone
with
unactivated
using
Mn
2
(CO)
10
as
catalyst
under
blue‐light
(457
nm)
irradiation
without
any
external
acid
or
base
pre‐functionalization
presented.
The
selective
tertiary
over
secondary
primary
bonds
in
abundant
feedstocks
was
achieved,
hydroxylation
quinones
realized
situ
by
employing
the
developed
methodology.
This
protocol
provides
new
catalytic
system
for
direct
construction
high‐value‐added
compounds,
namely,
parvaquone
(a
commercially
available
drug
used
treat
theileriosis
)
derivatives
ambient
reaction
conditions.
Moreover,
this
operationally
simple
applies
linear‐,
branched‐,
cyclo‐alkanes
degrees
site
selectivity
irradiated
conditions
could
provide
rapid
straightforward
access
versatile
methodologies
upgrading
feedstock
chemicals.
Mechanistic
insight
radical
trapping,
scavenging,
EPR,
other
controlled
experiments
well
corroborated
DFT
studies
suggest
that
proceeds
pathway.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(23), P. 16410 - 16423
Published: Nov. 9, 2023
Three-component
alkene
1,2-difunctionalizations
have
emerged
as
a
powerful
strategy
for
rapid
buildup
of
diverse
and
complex
alkylpyridines,
but
the
distal
functionalized
alkyl
radicals
1,2-alkylpyridylations
were
still
rare.
Herein,
we
report
an
example
regioselective
three-component
1,2-cyanoalkylpyridylation
feedstock
styrenes
with
accessible
nonredox-active
cyclic
oximes
through
visible-light
photoredox
catalysis,
providing
series
structurally
β-cyanoalkylated
alkylpyridines.
This
protocol
proceeds
radical
relay
pathway
including
generation
iminyl
enabled
by
phosphoranyl
radical-mediated
β-scission,
transposition
C-C
bond
cleavage,
highly
selective
addition,
precise
radical-radical
cross-coupling
sequence,
thus
facilitating
formation
two
distinct
single
bonds
in
single-pot
operation.
synthetic
features
mild
conditions,
broad
compatibility
functional
groups
substrate
scope,
product
derivatization,
late-stage
modification.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 4, 2024
Difluoromethylene
and
pyridine
cores
are
very
important
structural
units
in
medicinal
chemistry.
Herein,
we
report
the
development
of
photoredox-catalyzed
ring-opening
1,3-alkoxypyridylation
gem-difluorinated
cyclopropanes
using
4-cyanopyrines
alcohols,
employing
cyclopropane
radical
cations
as
key
intermediate.
The
reaction
exhibits
high
regioselectivity
under
mild
conditions
can
also
be
practiced
on
gram-scale
synthesis,
telescoped
reaction,
late-stage
functionalization
biological
molecules.
