Organic Letters,
Journal Year:
2018,
Volume and Issue:
20(15), P. 4579 - 4583
Published: July 19, 2018
An
efficient
and
mild
zinc-mediated
decarboxylative
alkylation
of
gem-difluoroalkenes
with
N-hydroxyphthalimide
(NHP)
esters,
to
give
monofluoroalkenes
in
moderate
excellent
yields
high
Z-selectivity
is
reported.
The
reaction
tolerates
a
broad
range
functional
groups
can
be
easily
scaled
up,
which
thus
may
pave
the
way
for
its
further
applications
medicinal
chemistry
materials
science.
Chemical Reviews,
Journal Year:
2018,
Volume and Issue:
119(4), P. 2192 - 2452
Published: Nov. 27, 2018
C–H
activation
has
surfaced
as
an
increasingly
powerful
tool
for
molecular
sciences,
with
notable
applications
to
material
crop
protection,
drug
discovery,
and
pharmaceutical
industries,
among
others.
Despite
major
advances,
the
vast
majority
of
these
functionalizations
required
precious
4d
or
5d
transition
metal
catalysts.
Given
cost-effective
sustainable
nature
earth-abundant
first
row
metals,
development
less
toxic,
inexpensive
3d
catalysts
gained
considerable
recent
momentum
a
significantly
more
environmentally-benign
economically-attractive
alternative.
Herein,
we
provide
comprehensive
overview
on
until
summer
2018.
Chemical Society Reviews,
Journal Year:
2018,
Volume and Issue:
47(17), P. 6603 - 6743
Published: Jan. 1, 2018
The
present
review
is
devoted
to
summarizing
the
recent
advances
(2015-2017)
in
field
of
metal-catalysed
group-directed
C-H
functionalisation.
In
order
clearly
showcase
molecular
diversity
that
can
now
be
accessed
by
means
directed
functionalisation,
whole
organized
following
directing
groups
installed
on
a
substrate.
Its
aim
comprehensive
reference
work,
where
specific
group
easily
found,
together
with
transformations
which
have
been
carried
out
it.
Hence,
primary
format
this
schemes
accompanied
concise
explanatory
text,
are
ordered
sections
according
their
chemical
structure.
feature
typical
substrates
used,
products
obtained
as
well
required
reaction
conditions.
Importantly,
each
example
commented
respect
most
important
positive
features
and
drawbacks,
aspects
such
selectivity,
substrate
scope,
conditions,
removal,
greenness.
targeted
readership
both
experts
functionalisation
chemistry
(to
provide
overview
progress
made
last
years)
and,
even
more
so,
all
organic
chemists
who
want
introduce
way
thinking
for
design
straightforward,
efficient
step-economic
synthetic
routes
towards
molecules
interest
them.
Accordingly,
should
particular
also
scientists
from
industrial
R&D
sector.
overall
goal
promote
application
reactions
outside
research
dedicated
method
development
establishing
it
valuable
archetype
contemporary
R&D,
comparable
role
cross-coupling
play
date.
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
58(2), P. 390 - 402
Published: June 28, 2018
Abstract
The
activation
of
carbon–fluorine
(C−F)
bonds
is
an
important
topic
in
synthetic
organic
chemistry.
Metal‐mediated
and
‐catalyzed
elimination
β‐
or
α‐fluorine
proceeds
under
milder
conditions
than
oxidative
addition
to
C−F
bonds.
initiated
from
organometallic
intermediates
having
fluorine
substituents
on
carbon
atoms
β
α
metal
centers,
respectively.
Transformations
through
these
processes
(C−F
bond
cleavage),
which
are
typically
preceded
by
carbon–carbon
(or
carbon–heteroatom)
formation,
have
been
increasingly
developed
the
past
five
years
as
methods.
In
this
Minireview,
we
summarize
applications
transition‐metal‐mediated
chemistry
a
historical
perspective
with
early
studies
systematic
recent
studies.
Journal of the American Chemical Society,
Journal Year:
2017,
Volume and Issue:
139(36), P. 12632 - 12637
Published: Aug. 29, 2017
Herein,
we
described
a
nickel-catalyzed
monofluoroalkenylation
through
defluorinative
reductive
cross-coupling
of
gem-difluoroalkenes
with
alkyl
halides.
Key
to
the
success
this
strategy
is
combination
C–F
cleavage
halides
activation.
This
reaction
enables
convenient
synthesis
large
variety
functionalized
monofluoroalkenes
under
mild
conditions
broad
functional
group
compatibility
and
excellent
Z-selectivity.
The
Ni
catalysis
(Bpin)2/K3PO4
as
terminal
reductant
promoted
efficient
C(sp2)–C(sp3)
formation
especially
generation
all-carbon
quaternary
centers
high
chemoselectivity.
ACS Catalysis,
Journal Year:
2017,
Volume and Issue:
7(6), P. 4209 - 4213
Published: May 11, 2017
C–F/C–H
functionalizations
proved
to
be
viable
within
a
versatile
manganese(I)
catalysis
manifold.
Thus,
wealth
of
fluorinated
alkenes
were
employed
in
through
facile
C–H
activation.
The
robust
nature
the
regime
was
among
others
reflected
by
first
activation
with
perfluoroalkenes
as
well
racemization-free
on
imines,
amino
acids,
and
peptides.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(24), P. 17479 - 17646
Published: Oct. 14, 2022
Alkenes
and
their
derivatives
are
featured
widely
in
a
variety
of
natural
products,
pharmaceuticals,
advanced
materials.
Significant
efforts
have
been
made
toward
the
development
new
practical
methods
to
access
this
important
class
compounds
by
selectively
activating
alkenyl
C(sp2)–H
bonds
recent
years.
In
comprehensive
review,
we
describe
state-of-the-art
strategies
for
direct
functionalization
sp2
C–H
C–F
until
June
2022.
Moreover,
metal-free,
photoredox,
electrochemical
also
covered.
For
clarity,
review
has
divided
into
two
parts;
first
part
focuses
on
currently
available
using
different
alkene
as
starting
materials,
second
describes
bond
easily
accessible
gem-difluoroalkenes
material.
This
includes
scope,
limitations,
mechanistic
studies,
stereoselective
control
(using
directing
groups
well
metal-migration
strategies),
applications
complex
molecule
synthesis
where
appropriate.
Overall,
aims
document
considerable
advancements,
current
status,
emerging
work
critically
summarizing
contributions
researchers
working
fascinating
area
is
expected
stimulate
novel,
innovative,
broadly
applicable
functionalizations
coming
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(16), P. 8903 - 8953
Published: Jan. 1, 2021
The
formation
of
C–aryl
bonds
has
been
the
focus
intensive
research
over
last
decades
for
construction
complex
molecules
from
simple,
readily
available
feedstocks.
National Science Review,
Journal Year:
2017,
Volume and Issue:
4(3), P. 303 - 325
Published: May 1, 2017
Abstract
The
new
millennium
has
witnessed
the
rapid
development
of
synthetic
organofluorine
chemistry
all
over
world,
and
chemists
in
China
have
made
significant
contributions
this
field.
This
review
aims
to
provide
a
brief
introduction
China's
primary
innovations
from
2000
early
2017,
covering
fluorination,
fluoroalkylation,
fluoromethylthiolation,
fluoroolefination
polyfluoroarylation,
as
well
synthesis
with
fluorinated
building
blocks.
Recent
advances
difluorocarbene
carbon–fluorine
bond
activation
are
also
discussed.
As
conclusion,
ends
some
personal
perspectives
on
future
chemistry.
Angewandte Chemie International Edition,
Journal Year:
2017,
Volume and Issue:
56(43), P. 13342 - 13346
Published: Aug. 31, 2017
A
copper
catalytic
system
was
established
for
the
stereoselective
hydrodefluorination
of
gem-difluoroalkenes
through
C-F
activation
to
synthesize
various
Z
fluoroalkenes.
H2
O
is
used
as
hydrogen
source
fluorine
acceptor
moiety.
This
mild
shows
good-functional
group
compatibility,
accepting
a
range
carbonyls
precursors
gem-difluoroalkenes,
including
aliphatic,
aromatic,
and
α,β-unsaturated
aldehydes
even
ketones.
It
serves
powerful
synthetic
method
late-stage
modification
complex
compounds.
