European Journal of Organic Chemistry,
Год журнала:
2021,
Номер
2021(41), С. 5618 - 5622
Опубликована: Окт. 13, 2021
Abstract
As
a
simple
and
efficient
system,
Cu(OAc)
2
⋅
H
O
K
S
8
can
activate
‐phosphonates
to
produce
the
corresponding
dialkyl
phosphoryl
radicals.
The
obtained
radicals
react
smoothly
with
2‐amino‐1,4‐naphthoquinones,
affording
accurate
preparation
of
various
phosphoryl‐functionalized
2‐amino‐1,4‐naphthoquinones.
developed
copper‐catalyzed
cross‐dehydrogenative
phosphorylation
features
broad
substrate
scope,
easily
available
reagents,
high
atom
economy
operational
simplicity,
which
enables
practical
avenue
for
C−P
bond
formation.
ACS Catalysis,
Год журнала:
2023,
Номер
13(12), С. 7756 - 7794
Опубликована: Май 25, 2023
A
selection
of
perfluoroalkylation
reactions
aliphatic
substrates
that
display
methodological
and
synthetic
amplitude
will
be
studied,
giving
examples
their
applications
mechanistic
details.
An
array
approaches
for
fluoroalkylation
are
documented;
in
particular,
radical
protocols
prominent
among
methods.
To
effect,
addition
perfluoroalkyl
radicals
RF
(RF=CnF2n+1,
n
>
1)
to
unsaturated
organic
serve
as
one
the
most
direct
efficacious
ways
access
fluoroalkylated
scaffolds.
The
syntheses
perfluoroalkyl-substituted
vinyl,
alkynyl,
allylic
compounds;
hydro-,
iodo-,
oxy-perfluoroalkylated
alkanes
olefins;
carbonyl
enamides,
amides,
thioamides,
hydrazones;
multicomponent
studied.
While
there
a
number
accomplished
reports
on
organofluorination,
we
aim
provide
an
overview
radical-involved
substrates,
covering
from
2018
early
2023,
summarized
Tables
1–4.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(27)
Опубликована: Май 21, 2024
Abstract
The
direct
functionalization
of
quinones
has
always
fascinated
research
communities
due
to
their
biological
and
redox
activities
subsequent
application.
Quinone
motifs
play
a
vital
role
as
precursors
for
many
bioactive
compounds
materials;
hence,
ingenious
methodologies
have
been
elaborated
exploring
these
units.
A
significant
part
the
synthetic
strategies
towards
functionalized
achieved
by
installing
substituents
on
hydroquinones,
phenols,
or
quinone
itself
different
oxidative
coupling
reactions
via
radical
pathways
with
without
utilization
metal
catalysts.
simple
C−H
bond
remains
challenging
inherited
electronic
nature
high
dissociation
energy.
This
review
article
summarizes
recent
advancement
made
through
quinones.
Our
primary
focus
will
be
approaches
mechanistic
that
appeared
in
last
two
decades,
along
short
historical
importance
family.
Asian Journal of Organic Chemistry,
Год журнала:
2021,
Номер
10(12), С. 3201 - 3232
Опубликована: Ноя. 5, 2021
Abstract
Olefins
are
synthetically
useful
building
blocks
in
modern
organic
synthesis.
Direct
functionalization
of
olefins;
represent
one
the
most
explored
transformations
synthetic
chemistry
due
to
their
easy
availability
and
reactivity
towards
large
number
reactants
affording
diverse
range
compounds.
In
recent
times,
development
new
protocols
for
olefins
is
a
growing
realm.
A
plethora
olefin
methodologies
have
been
reported
literature
through
ionic
free
radical
mechanisms
including
single
electron
transfer
(SET)
last
two
decades.
This
review
gives
an
overview
mono‐
difunctionalization
unactivated
olefins,
with
emphasis
on
mechanistic
details.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(11), С. 7401 - 7424
Опубликована: Май 12, 2023
Herein,
we
report
a
blue-light-driven
amination
of
C(sp2)-H
bond
naphthoquinones
and
quinones
with
the
N-H
primary
secondary
amines
for
synthesis
2-amino-naphthoquinones
2-amino-quinones.
The
coupling
wide
array
aliphatic,
aromatic,
chiral,
primary,
having
electron
donating
(-CH3,
-OCH3,
-SCH3),
withdrawing
(-F,
-Cl,
-Br,
-I),
CO2H,
-OH,
-NH2
groups
acidic
protons
selectively
occurred
to
afford
C-N
coupled
in
60-99%
yields
hydrogen
gas
as
byproduct
methanol
solvent
without
using
any
additional
reagents,
additives,
oxidant
under
blue
light
irradiation.
Mechanistic
insight
by
DFT
computation,
controlled
experiments,
kinetic
isotopic
effect,
substitution
effect
substrates
suggest
that
reaction
proceeds
radical
pathway
which
naphthoquinone
forms
highly
oxidizing
naphthoquinonyl
biradical
upon
irradiation
(457
nm).
Consequently,
transfer
from
electron-rich
amine
an
leads
anion
aminyl
cation,
followed
proton
delocalization
leading
carbon-centered
radical.
cross-coupling
nitrogen
radicals
bond,
subsequent
elimination
(which
was
also
confirmed
GC-TCD),
affording
2-amino-1,4-naphthoquinone
metal-,
reagent-,
base-,
oxidant-free
conditions.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(13), С. 2092 - 2125
Опубликована: Май 16, 2023
Abstract
Fluorinated
alkyl
iodides
serve
as
a
convenient
and
inexpensive
source
of
fluoroalkyl
radicals
that
can
readily
undergo
addition
to
the
C−C
unsaturated
bonds
alkynes
alkenes
which
is
foundation
for
variety
useful
synthetic
protocols.
Since
2010
this
field
has
witnessed
huge
progress
in
several
respects.
First
portfolio
fluorinated
was
extended
beyond
only
simple
perfluoroalkyl
(C
n
F
2n+1
I).
In
particular,
employment
iododifluoro−methyl‐
carbonyls
phosphonates
enabled
facile
installation
medicinally
relevant
difluoromethylene
motif.
Secondly,
from
conceptual
point
view,
novel
strategies
activation
towards
radical
formation
have
been
introduced,
relying
on
electron
donor‐acceptor
(EDA)
complexes,
photoredox
catalysis,
frustrated
Lewis
pairs
transition
metal
complementing
prior
approaches
based
heat
UV
induced
C−I
homolysis,
initiators,
transfer
processes.
Based
these
range
fluoroalkylative
transformations
systems
added
classical
iodoperfluoroalkylation.
Broadly
applicable
protocols
fluoroalkylation
hydrofluoroalkylation,
well
more
sophisticated,
complexity‐building
methods
fluoroalkylation‐annulation
tandem
multicomponent
fluoroalkylations
with
concomitant
another
functionality
recently
disclosed.
This
review
summarizes
achieved
since
reactivity
emphasis
placed
above‐mentioned
advances.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(17), С. 4708 - 4715
Опубликована: Янв. 1, 2024
A
simple
and
practical
visible
light-driven
photoredox-catalyzed
three-component
carbotrifluoromethylation
of
alkenes
is
revealed
for
the
synthesis
1,4-bis(trifluoromethylated)
compounds.
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(11), С. 7274 - 7290
Опубликована: Май 20, 2022
The
first
Fe-catalyzed
three-component
radical
trifluoromethyl-alkenylation
of
alkenes
with
2-amino-1,4-naphthoquinones
and
CF3SO2Na
is
reported.
developed
reaction
enables
the
highly
regioselective
preparation
a
variety
valuable
CF3-substituted
1,4-naphthoquinones
in
acceptable
yields.
In
light
catalytic
system,
alkynes
smoothly
afford
corresponding
three-
or
four-component
products.
This
protocol
features
use
easily
available
inexpensive
reagents,
broad
substrate
scope,
simple
conditions.
Chemistry - An Asian Journal,
Год журнала:
2021,
Номер
16(17), С. 2417 - 2420
Опубликована: Июль 8, 2021
Abstract
A
gold‐catalyzed
synthesis
of
polyfluoroalkylated
oxazoles
from
N‐propargylamides
under
visible‐light
irradiation
has
been
developed.
These
reactions
display
excellent
compatibility
radicals
and
gold
catalysts
irradiation.
Mechanistic
experiments
indicate
that
polyfluoroalkyl
iodides
play
a
dual
role
in
enhanced
through
assisted
protodeauration
vinyl
reactivated
the
catalyst.
In
addition,
PPh
3
AuNTf
2
not
only
activates
N‐propargylamide
to
generate
intermediate,
but
also
greatly
promotes
homolysis
blue
light
