Abstract
The
difluoromethyl
group
(CF2H)
can
function
as
a
lipophilic
hydrogen-bond
donor,
and
is
regarded
bioisostere
of
functional
groups
such
hydroxy
(-OH),
thiol
(-SH),
amino
(-NH2).
unique
physicochemical
properties
this
make
difluoromethylation
hot
topic
in
the
field
synthetic
organic
chemistry,
recent
decades,
various
methods
have
been
developed
for
constructing
C(sp3)—CF2H,
C(sp2)—CF2H,
C(sp)
—CF2H,
X—CF2H
(X
=
N,
O,
S,
Se,
B,
P,
etc.)
bonds.
This
review
summarizes
currently
available
reagents
performing
reactions,
well
other
approaches
installing
unit.
Organic Letters,
Год журнала:
2023,
Номер
25(45), С. 8127 - 8132
Опубликована: Ноя. 3, 2023
We
report
herein
a
highly
efficient
copper-catalyzed
protocol
for
the
transformation
of
haloalkynes
to
corresponding
difluoromethylated
alkynes.
This
scalable
exhibits
broad
substrate
scope
and
excellent
functional
group
tolerance,
enabling
late-stage
difluoromethylation
bioactive
molecules.
Additionally,
strategy
utilizing
difluoromethylalkynes
in
gram-scale
reactions
multiple
transformations
has
proven
be
valuable
synthetic
chemistry.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
89(1), С. 565 - 575
Опубликована: Дек. 20, 2023
An
array
of
biologically
interesting
tri/difluoromethylated
chromones
and
their
heteroatom
analogues
were
conveniently
synthesized
from
the
reaction
with
CF3SO2Na
or
HCF2SO2Na
in
presence
tert-butyl
hydroperoxide
under
mild
conditions.
A
mechanistic
pathway
involving
generation
electrophilic
tri/difluoromethyl
radical,
followed
radical
substitution
analogues,
was
postulated.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(46)
Опубликована: Авг. 9, 2024
Abstract
Given
the
prevalence
of
pyridine
motifs
in
FDA‐approved
drugs,
selective
fluoroalkylation
pyridines
and
quinolines
is
essential
for
preparing
diverse
bioisosteres.
However,
challenges
are
often
faced
with
conventional
Minisci
reactions
achieving
precise
regioselectivity
owing
to
competing
reaction
sites
limited
availability
fluoroalkyl
radical
sources.
Herein,
we
present
a
light‐driven,
C4‐selective
azines
utilizing
N‐aminopyridinium
salts
readily
available
sulfinates.
Our
approach
employs
electron
donor‐acceptor
complexes,
highly
under
mild
conditions
without
an
external
photocatalyst.
This
practical
method
not
only
enables
installation
CF
2
H
groups
but
also
allows
incorporation
‐alkyl
functional
entities,
surpassing
limitations
previous
methods.
The
versatility
pathway
further
demonstrated
through
straightforward
three‐component
involving
alkenes
[1.1.1]propellane.
Detailed
experimental
computational
studies
have
elucidated
origins
regioselectivity,
providing
profound
insights
into
mechanistic
aspects.
Abstract
The
difluoromethyl
group
(CF2H)
can
function
as
a
lipophilic
hydrogen-bond
donor,
and
is
regarded
bioisostere
of
functional
groups
such
hydroxy
(-OH),
thiol
(-SH),
amino
(-NH2).
unique
physicochemical
properties
this
make
difluoromethylation
hot
topic
in
the
field
synthetic
organic
chemistry,
recent
decades,
various
methods
have
been
developed
for
constructing
C(sp3)—CF2H,
C(sp2)—CF2H,
C(sp)
—CF2H,
X—CF2H
(X
=
N,
O,
S,
Se,
B,
P,
etc.)
bonds.
This
review
summarizes
currently
available
reagents
performing
reactions,
well
other
approaches
installing
unit.
