Handbook of CH‐Functionalization,
Год журнала:
2022,
Номер
unknown, С. 1 - 68
Опубликована: Ноя. 29, 2022
Abstract
This
article
summarizes
the
main
recent
achievements
reported
in
transition
metal‐catalyzed
and
metal‐free
CH
difluoromethylation
perfluoroalkylation
using
various
fluoroalkyl‐coupling
partners
over
past
decade,
for
constructing
high‐valuable
fluoro‐containing
heteroarenes.
resume
is
mainly
categorized
based
on
different
catalytic
systems
each
fluoroalkylation
reaction.
Difluoroalkylation
that
involves
a
or
visible‐light‐induced
reaction
will
be
addressed
first.
Following
this,
direct
of
bonds
under
conditions
covered.
The
overall
aim
to
paint
picture
state
art
difluoro‐
chemistry
medicinal
chemists
point
out
how
innovative
strategies
have
been
able
positively
affect
synthesis
new
bioactive
compounds.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
28(41)
Опубликована: Май 11, 2022
Abstract
Perfluoroalkylated
(hetero)arenes
represent
an
extremely
important
family
of
molecules
commonly
utilized
in
many
areas
such
as
medicinal
chemistry,
agrochemistry
and
material
sciences.
Due
to
their
unique
properties,
they
have
attracted
significant
interest
from
synthetic
chemists
various
methods
been
developed
for
synthesis.
Among
them,
the
direct
perfluoroalkylation
C(sp
2
)−H
bonds
is
one
most
attractive
straightforward
ones,
provided
that
it
proceeds
with
high
levels
regioselectivity.
In
this
review
article,
a
comprehensive
overview
advances
field
presented,
special
focus
on
reaction
mechanisms
involved
these
transformations
All
available
classified
according
nature
perfluoroalkyl
chain
introduced,
trifluoromethylation
reactions
being
overviewed
separate
section,
reagents/catalysts
required.
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(5), С. 3788 - 3793
Опубликована: Фев. 21, 2022
A
novel
tetrahydroxydiboron
and
nickel
chloride
cocatalyzed
radical
cyclization
cascade
with
a
broad
substrate
scope
an
ultrashort
reaction
time
was
developed.
The
mechanistic
investigation
indicated
that
the
might
involve
homocleavage
of
hydride
intermediates.
This
approach
enables
simple
efficient
synthesis
series
heteropolycycles.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(21), С. 5790 - 5797
Опубликована: Янв. 1, 2022
A
photo-induced,
catalytic
PPh
3
-promoted
perfluoroalkylation
reaction
of
indole
molecules
is
developed
to
give
perfluoroalkylated
products
in
moderate
excellent
yields,
which
13
F-containing
indoles
exhibited
good
antibacterial
activities.
A
mechanochemical
strategy
for
promoting
copper‐catalyzed
solid‐state
radical
C–H
difluoroalkylation
reactions
has
been
devised.
Compared
to
traditional
solution‐based
methods,
this
mechanoredox
approach
offers
enhanced
ease
of
handling,
greater
cleanliness,
and
improved
sustainability
the
synthesis
difluoroalkylated
indoles,
which
constitute
crucial
structural
motifs
in
contemporary
drug
discovery.
The
underlying
reaction
mechanism
is
investigated
through
meticulous
step‐by‐step
control
experiments
that
highlighted
substantial
influence
conditions.
versatility
protocol
demonstrated
by
its
applications
complex
natural
products
derivatives.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(16), С. 4435 - 4440
Опубликована: Янв. 1, 2022
The
regioselective
C–H
heptafluoroisopropylation
of
heteroarenes
with
heptafluoroisopropyl
silver
provided
convenient
access
to
a
wide
range
CF(CF
3
)
2
-containing
heteroarenes.
Communications Chemistry,
Год журнала:
2023,
Номер
6(1)
Опубликована: Авг. 24, 2023
The
isoperfluoropropyl
group
(i-C3F7)
is
an
emerging
motif
in
pharmaceuticals,
agrichemicals
and
functional
materials.
However,
isoperfluoropropylated
compounds
remain
largely
underexplored,
presumably
due
to
the
lack
of
efficient
access
these
compounds.
Herein,
we
disclose
practical
isoperfluoropropylation
aromatic
C-H
bonds
through
invention
a
hypervalent-iodine-based
reagent-PFPI
reagent,
that
proceeds
via
Ag-X
coupling
process.
activation
PFPI
reagent
without
any
catalysts
or
additives
was
demonstrated
synthesis
electron-rich
heterocycles,
while
its
activity
under
photoredox
catalysis
shown
non-activated
arenes.
Detailed
mechanistic
experiments
DFT
calculations
revealed
SET-induced
concerted
pathway
reactions.
In
addition,
unique
conformation
i-C3F7
products,
involved
intramolecular
hydrogen
bond
investigated
by
X-ray
single-crystal
diffraction
variable-temperature
NMR
experiments.
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(14), С. 9128 - 9138
Опубликована: Июль 6, 2022
An
efficient
method
for
C3-fluoroalcoholation
of
indole
derivatives
was
developed
by
merging
C–F
cleavage
and
C–C
bond
coupling,
using
free
(NH)-indoles
heptafluoroisopropyl
iodides
as
precursors.
Preliminary
mechanistic
studies
indicate
that
the
bimetallic
co-mediated
trifluoroacetate
moiety
play
an
essential
role.
Notably,
this
strategy
constructs
derivatizations
through
modifiable
carbon–oxygen
bond.
A
broad
range
structurally
valuable
organofluorine
products
obtained,
which
shows
excellent
functional
group
tolerance.
Furthermore,
easily
accessible
materials
were
utilized
circumvented
two
troublesome
steps
installing
removing
external
auxiliary.
This
is
first
report
to
introduce
3-fluoroalcoholated
indoles
via
fluorohalides.
reaction
offers
a
straightforward
platform
access
worthwhile
fluorinated
(NH)-heteroarenes
derivatives.
