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.
The Chemical Record,
Journal Year:
2023,
Volume and Issue:
23(9)
Published: May 22, 2023
Abstract
In
the
last
few
years,
many
reagents
and
protocols
have
been
developed
to
allow
for
efficient
fluorofunctionalization
of
a
diverse
set
scaffolds
ranging
from
alkanes,
alkenes,
alkynes,
(hetero)arenes.
The
concomitant
rise
organofluorine
chemistry
visible
light‐mediated
synthesis
synergistically
expanded
fields
mutually
benefitted
developments
in
both
fields.
this
context,
light
driven
formations
radicals
containing
fluorine
major
focus
discovery
new
bioactive
compounds.
This
review
details
recent
advances
progress
made
fluoroalkylation
heteroatom
centered
radical
generation.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(4), P. 635 - 697
Published: Jan. 13, 2024
Abstract
In
recent
years,
the
interest
to
develop
cyclizations
promoted
by
visible
light
has
been
gaining
a
lot
of
attention
due
its
sustainability
aspect.
this
review,
we
summarize
most
important
advances
in
period
describing
methods
used
generate
different
ring
sizes,
while
focusing
on
mechanistic
details
these
reactions.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(5), P. 1158 - 1164
Published: Jan. 10, 2024
Abstract
A
visible‐light‐promoted
cascade
difluoromethylation/cyclization
reaction
to
access
various
difluoromethylated
pyrrolo[1,2‐
a
]indolediones
was
developed
using
difluoromethyltriphenylphosphonium
bromide
salt
as
the
difluoromethylating
reagent.
possible
radical
mechanism
has
been
investigated
and
proven
single
electron
transfer
(SET)
procedure.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(5), P. 2815 - 2824
Published: Feb. 22, 2024
The
emergence
of
photocatalysis
has
greatly
advanced
radical
fluoroalkylation
reactions.
Central
to
this
advancement
is
the
introduction
and
refinement
reagents,
which
play
a
pivotal
role
in
driving
these
reactions
forward.
Intriguingly,
some
previously
not
recognized
for
their
properties,
have
emerged
as
key
players
area.
In
Perspective,
we
provide
an
overview
four
representative
reagents
pioneered
by
our
laboratory,
subsequently
garnered
extensive
application
broader
research
contexts,
including
difluorocarbene
precursors
bromodifluoromethylphosphonium
bromide,
electrophilic
sulfonylation
reagent
triflic
anhydride,
nucleophilic
trifluoromethylation
methyl
fluorosulfonyldifluoroacetate
(Chen's
reagent).
integration
phosphonium
into
enabled
unexpected
reactivities
now
notably
expanded
capabilities
difluoromethylation,
trifluoromethylation,
difluoroalkylation.
Our
discussion
highlights
how
atypical
enriched
toolkit
available
fluoroalkylations,
offering
insights
that
could
inspire
future
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(16), P. 6188 - 6193
Published: Jan. 1, 2023
A
metal-free
photocatalytic
radical
annulation
of
2-cyanoaryl
acrylamides
with
[CF
2
HPPh
3
]
+
Br
−
to
give
4-amino-quinolinones
in
good
yields
was
developed.
An
easily
obtained
organophotocatalyst
and
green
solvent
acetone/H
O
were
utilized
the
protocol.
ACS Omega,
Journal Year:
2024,
Volume and Issue:
9(26), P. 28129 - 28143
Published: June 19, 2024
An
efficient
and
mild
protocol
for
the
visible
light-induced
radical
cascade
difluoromethylation/cyclization
of
imidazoles
with
unactivated
alkenes
using
easily
accessible
bench-stable
difluoromethyltriphenylphosphonium
bromide
as
precursor
-CF
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(4), P. 872 - 876
Published: Jan. 18, 2024
A
new
difluoroalkylation
reagent
Sulfox-CF2SO2Ph
bearing
both
sulfoximine
and
sulfone
moieties
was
prepared
from
commercially
available
SulfoxFluor
PhSO2CF2H.
On
one
hand,
the
could
act
as
a
(phenylsulfonyl)difluoromethyl
radical
source
under
photoredox
catalysis,
in
which
arylsulfoximidoyl
group
is
selectively
removed.
other
basic
conditions,
serve
difluorocarbene
precursor
for
S-
O-difluoromethylations
with
O-nucleophiles,
respectively,
phenylsulfonyl
removed
(followed
by
α-elimination
of
group).
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(24), P. 17134 - 17143
Published: Dec. 6, 2023
It
is
significant
to
develop
novel
difluoromethylation
methods
because
of
the
important
roles
difluoromethyl
groups
in
medicinal
chemistry
and
material
industries.
Here,
we
developed
a
difluoromethylation–carboxylation
difluoromethylation–deuteration
method
triggered
by
radical
generated
electroreduction
stable
easily
available
difluoromethyltriphenylphosphonium
bromide.
Various
molecules
containing
carboxyl
or
deuterium
can
be
synthesized
through
this
method.
The
establishment
will
provide
an
alternative
reactions.
A
convenient
visible-light-promoted
difluoromethylation/cyclization
reaction
to
access
various
difluoromethylated
benzo[4,5]imidazo[2,1-
a
]isoquinolin-6(5
H
)-ones
was
developed
using
[Ph
3
PCF
2
H]
+
Br
−
as
reagent.
