Organic Letters,
Journal Year:
2020,
Volume and Issue:
22(4), P. 1414 - 1419
Published: Feb. 3, 2020
Herein,
we
describe
a
palladium-catalyzed
alkynylation
of
gem-difluorinated
cyclopropanes
via
C–C
bond
activation/C–F
cleavage,
followed
by
C–C(sp)
coupling.
The
new
approach
proceeds
with
broad
substrate
scope
under
mild
reaction
conditions,
whereas
both
1,1-disubstituted
and
complex-molecule-modified
react
smoothly
high
stereoselectivity.
developed
method
provides
efficient
convenient
ways
access
to
diversity
important
fluorinated
enynes
arenes
slightly
modification
the
conditions.
Chemical Science,
Journal Year:
2018,
Volume and Issue:
10(3), P. 809 - 814
Published: Nov. 7, 2018
Synthesis
of
functionalized
gem-difluoroalkenes
was
achieved
through
nickel-catalyzed
allylic
defluorinative
alkylation
trifluoromethyl
alkenes
with
reductive
decarboxylation
redox-active
esters.
Chemical Communications,
Journal Year:
2019,
Volume and Issue:
55(90), P. 13486 - 13505
Published: Jan. 1, 2019
α-Trifluoromethylstyrene
derivatives
are
versatile
synthetic
intermediates
for
the
preparation
of
more
complex
fluorinated
compounds.
Much
attention
has
been
paid
to
these
compounds
by
organic
chemistry
community,
because
they
have
successfully
utilized
in
C-F
bond
activation
a
CF3
group,
mainly
including
anionic
SN2'-type
substitution,
cationic
SN1'-type
ipso-substitution
and
defluorinative
functionalization
with
transition
metals
or
photoredox
catalysts.
In
addition,
metal-catalyzed
cycloaddition
reactions
α-trifluoromethylstyrenes
developed
construction
cycloalkanes
cycloalkenes
containing
fluoro
trifluoromethyl
groups.
this
review,
we
systematically
summarized
synthesis
their
applications
chemistry,
mechanisms
were
also
discussed.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(17), P. 6395 - 6400
Published: April 27, 2021
A
site-selective
defluorinative
sp3
C–H
alkylation
of
secondary
amides
that
rapidly
and
reliably
incorporates
gem-difluoroalkene
motifs
into
previously
unfunctionalized
sites
is
disclosed.
This
protocol
distinguished
by
its
mild
conditions,
wide
scope,
exquisite
site-selectivity,
thus
unlocking
a
new
platform
to
introduce
carbonyl
isosteres
at
saturated
hydrocarbon
sites.
Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
364(2), P. 234 - 267
Published: Nov. 29, 2021
Abstract
Fluorine‐containing
moieties
are
widely
used
in
the
pharmaceutical,
agrochemical,
and
material
fields.
Thus,
these
structures
of
immense
interest
fields
organic
synthesis
medicinal
chemistry.
Among
various
fluorinated
groups,
difluoromethyl
unit
has
drawn
increasing
attention
due
to
its
unique
pharmaceutical
properties.
In
recent
years,
several
methods
for
difluoromethylated
compounds
have
been
rapidly
developed.
However,
most
treat
aromatic
with
excess
difluoromethylating
reagents,
which
often
contain
organometallic
compounds,
so
transformations
generally
less
environmentally
friendly
atom‐economical.
this
review,
we
summarize
development
new
motifs
or
difluoroalkenes
from
trifluoromethylated
trifluoromethyl
alkenes
via
single
C(
sp
3
)−F
bond
cleavage.
magnified
image
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(27), P. 10282 - 10291
Published: June 24, 2021
Transition-metal-catalyzed
dicarbofunctionalization
of
alkenes
involving
intramolecular
Heck
cyclization
followed
by
intermolecular
cross-coupling
has
emerged
as
a
powerful
engine
for
building
heterocycles
with
sterically
congested
quaternary
carbon
centers.
However,
only
exo-cyclization/cross-coupling
products
can
be
obtained;
endo-selective
cyclization/cross-coupling
not
been
reported
yet
and
still
poses
formidable
challenge.
We
herein
report
the
first
example
catalyst-controlled
regiodivergent
synthesis
five-
six-membered
benzo-fused
lactams
bearing
all-carbon
Using
chiral
Pyrox-
or
Phox-type
bidentate
ligand,
5-exo
cyclization/cross-couplings
proceed
favorably
to
produce
indole-2-ones
in
good
yields
excellent
regioselectivity
enantioselectivities
(up
98%
ee).
When
C6-carboxylic
acid-modified
2,2′-bipyridine
was
used
3,4-dihydroquinolin-2-ones
were
obtained
through
6-endo-selective
processes.
This
transformation
is
modular
tolerant
variety
functional
groups.
The
ligand
rather
than
substrate
structures
precisely
dictates
pattern.
Moreover,
synthetic
value
this
protocol
demonstrated
preparation
biologically
relevant
molecules
structural
scaffolds.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(30), P. 11602 - 11610
Published: July 22, 2021
Herein
we
report
a
chromium-catalyzed
allylic
defluorinative
ketyl
olefin
coupling
between
aldehydes
and
α-trifluoromethyl
alkenes,
which
provides
novel
efficient
access
to
diverse
gem-difluorohomoallylic
alcohols.
Remarkably,
the
high
chemoselectivity
of
this
reaction
enables
conversion
formyl
moiety
in
presence
various
easily
reducible
functionalities
including
ketone,
organohalides,
aziridine,
sulfone,
alkyne,
unactivated
alkene.
The
utility
method
is
demonstrated
by
simple
derivatizations
attached
hydroxyl
group
products.
preliminary
mechanistic
investigations
suggest
pathway
with
rate-limiting
C–C
forming
step
followed
facile
β-fluoro
elimination.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(49)
Published: Aug. 22, 2023
Abstract
Much
progress
has
been
made
in
the
development
of
methods
to
both
create
compounds
that
contain
C−F
bonds
and
functionalize
bonds.
As
such,
are
becoming
common
versatile
synthetic
functional
handles.
This
review
summarizes
advantages
defluorinative
functionalization
reactions
for
small
molecule
synthesis.
The
coverage
is
organized
by
type
carbon
framework
fluorine
attached
mono‐
polyfluorinated
motifs.
main
challenges,
opportunities
advances
discussed
each
class
organofluorine.
Most
text
focuses
on
case
studies
illustrate
how
defluorofunctionalization
can
improve
routes
targets
or
properties
enable
unique
mechanisms
reactions.
broader
goal
showcase
incorporating
exploiting
design
routes,
improvement
specific
advent
new
methods.
Organic Letters,
Journal Year:
2019,
Volume and Issue:
21(10), P. 3769 - 3773
Published: May 7, 2019
A
visible-light-promoted
redox
neutral
γ,γ-difluoroallylation
of
cycloketone
oxime
ethers
with
trifluoromethyl
alkenes
through
C–C
and
C–F
bond
cleavage
has
been
achieved,
which
affords
various
cyano-substituted
gem-difluoroalkenes
in
generally
good
yields.
The
reaction
provides
a
facile
protocol
for
forming
gem-difluoroalkene
functionality
cyano
group
while
incorporating
them
into
one
molecule.
conversion
the
resulting
to
cyclic
monofluoroalkenes
via
second
was
also
described.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(13), P. 5398 - 5402
Published: Jan. 17, 2020
We
report
a
NiH-catalyzed
migratory
defluorinative
coupling
between
two
electronically
differentiated
olefins.
A
broad
range
of
unactivated
donor
olefins
can
be
joined
directly
to
acceptor
containing
an
electron-deficient
trifluoromethyl
substituent
in
both
intra-
and
intermolecular
fashion
form
gem-difluoroalkenes.
This
shows
site-
chemoselectivity
under
mild
conditions,
with
the
formation
tertiary
or
quaternary
carbon
center.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(10), P. 4793 - 4799
Published: Jan. 14, 2020
The
hydrodefluorination
of
CF3-substituted
alkenes
can
be
catalyzed
by
a
nickel(II)
hydride
bearing
pincer
ligand.
catalyst
loading
as
low
1
mol%.
gem-Difluoroalkenes
containing
number
functional
groups
formed
in
good
to
excellent
yields
radical
mechanism
initiated
H•
transfer
from
the
nickel
hydride.
relative
reactivity
various
substrates
supports
proposed
mechanism,
does
TEMPO
trapping
experiment.
