Angewandte Chemie International Edition,
Journal Year:
2017,
Volume and Issue:
56(33), P. 9872 - 9876
Published: June 24, 2017
Abstract
A
Pd‐catalyzed
fluoroarylation
of
gem
‐difluoroalkenes
with
aryl
halides
is
reported.
By
taking
advantage
the
in
situ
generated
α‐CF
3
‐benzylsilver
intermediates
derived
from
nucleophilic
addition
silver
fluoride
to
‐difluoroalkenes,
this
strategy
bypasses
use
a
strong
base,
thus
enabling
mild
and
general
synthetic
method
for
ready
access
non‐symmetric
α,α‐disubstituted
trifluoroethane
derivatives.
Chemistry - A European Journal,
Journal Year:
2017,
Volume and Issue:
23(59), P. 14676 - 14701
Published: June 20, 2017
Abstract
The
relevance
of
the
‐CF
2
H
moiety
has
attracted
considerable
attention
from
organic
synthetic
and
medicinal
chemistry
communities,
because
this
group
can
act
as
a
more
lipophilic
isostere
carbinol,
thiol,
hydroxamic
acid,
or
amide
groups.
Being
weakly
acidic,
CF
establish
hydrogen‐bonding
interactions
to
improve
binding
selectivity
biologically
active
compounds.
Therefore,
hydroxyl,
amino,
thio
substituents
lead
structures
are
routinely
replaced
by
motif
in
drug
discovery,
with
great
benefits
pharmacological
activity
drugs
candidates
agrochemicals.
Consequently,
late‐stage
introduction
is
sought‐after
strategy
designing
bioactive
Secondly,
but
nonetheless
relevant
meaningful,
study
pathways
introduce
−Y
(Y≠H,
F)
into
substrates
compounds
that
contain
functionality
have
also
found
vast
applications
other
areas,
such
fungicides,
insecticides,
etc.,
thus,
deserves
special
attention.
Although
emphasis
made
on
difluoromethylation
strategies
functionalize
different
families
compounds,
three
main
methodological
protocols
will
be
presented
review
article
for
Y
moieties
substrates:
i)
metal‐photoredox
catalysis;
ii)
through
transition
metal‐catalyzed
thermal
protocols;
iii)
transition‐metal‐free
strategies.
Chemistry - A European Journal,
Journal Year:
2015,
Volume and Issue:
21(37), P. 12836 - 12865
Published: July 14, 2015
Fluorine
chemistry
is
a
field
undergoing
tremendous
expansion.
Although
much
attention
has
been
paid
to
the
introduction
of
fluorine
atom
and
CF3
group,
less
interest
devoted
functionalized
fluorinated
building
blocks,
in
sharp
contrast
with
high
versatility
products.
In
this
Minireview,
most
relevant
methods
for
difluoromethylated
blocks
are
summarized.
Access
arenes,
alkenes,
alkynes
highlighted
special
explanation
reaction
mechanism.
Angewandte Chemie International Edition,
Journal Year:
2016,
Volume and Issue:
55(8), P. 2934 - 2938
Published: Jan. 21, 2016
The
first
gold-catalyzed
photoredox
C(sp(2)
)-H
difluoroalkylation
and
perfluoroalkylation
of
hydrazones
with
readily
available
RF
-Br
reagents
is
reported.
resulting
gem-difluoromethylated
perfluoroalkylated
are
highly
functionalized,
versatile
molecules.
A
mild
reduction
the
coupling
products
can
efficiently
produce
β-amino
phosphonic
acids
acid
derivatives.
In
mechanistic
studies,
a
difluoroalkyl
radical
intermediate
was
detected
by
an
EPR
spin-trapping
experiment,
indicating
that
pathway
operating.
Asian Journal of Organic Chemistry,
Journal Year:
2016,
Volume and Issue:
6(2), P. 139 - 152
Published: Dec. 19, 2016
Abstract
Owing
to
the
excellent
performance
of
fluorinated
compounds
in
areas
pharmaceuticals,
agrochemicals,
and
materials
chemistry,
organic
chemists
have
made
great
efforts
towards
selective
incorporation
fluorine
or
moieties
into
molecules
through
nucleophilic,
electrophilic,
radical,
metal‐catalyzed
pathways.
Impressive
progress
fluorination
perfluoroalkylation
(especially
trifluoromethylation)
reactions
has
been
over
past
few
decades.
However,
methods
for
incorporating
lightly
groups
(such
as
−CF
2
H)
are
still
underdeveloped,
spite
their
important
applications
pharmaceuticals
agrochemicals.
This
Focus
Review
summarizes
recent
developments
direct
difluoromethylation
reactions.
Angewandte Chemie International Edition,
Journal Year:
2014,
Volume and Issue:
53(37), P. 9909 - 9913
Published: July 17, 2014
Abstract
Transition‐metal‐catalyzed
difluoroalkylation
of
aromatics
remains
challenging
despite
the
importance
difluoroalkylated
arenes
in
medicinal
chemistry.
Herein,
first
successful
example
nickel‐catalyzed
aryl
boronic
acids
is
described.
The
reaction
allows
access
to
a
variety
functionalized
difluoromethyl
bromides
and
chlorides,
paves
way
highly
cost‐efficient
synthesis
wide
range
arenes.
notable
features
this
protocol
are
its
high
generality,
excellent
functional‐group
compatibility,
low‐cost
nickel‐catalyst,
practicality
for
gram‐scale
production,
thus
providing
facile
method
applications
drug
discovery
development.
Organic Process Research & Development,
Journal Year:
2020,
Volume and Issue:
24(4), P. 470 - 480
Published: March 5, 2020
Fluorinated
organic
molecules
are
increasingly
being
prepared
for
a
variety
of
applications,
including
pharmaceutical
products.
However,
the
supply
chain
to
access
necessary
raw
materials,
which
originate
primarily
from
calcium
fluoride,
is
often
not
considered,
may
be
difficult
at
commercial
scale,
and
has
become
destabilized
as
more
stringent
environmental
policies
justifiably
enforced.
This
manuscript
presents
an
overview
preparation
use
simple
organofluorinated
intermediates
reagents
challenges
associated
with
them.
Organic Letters,
Journal Year:
2014,
Volume and Issue:
16(11), P. 2958 - 2961
Published: May 9, 2014
A
novel
method
for
visible-light
photoredox-catalyzed
difluoromethylation
of
electron-rich
N-,
O-,
and
S-containingheteroarenes
under
mild
reaction
conditions
is
developed.
Mechanistic
investigation
indicates
that
the
net
C–H
proceeds
through
an
electrophilic
radical-type
pathway.
